JP2011111678A - Method for forming conversion coating on outer surface of magnesium or magnesium alloy - Google Patents
Method for forming conversion coating on outer surface of magnesium or magnesium alloy Download PDFInfo
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- JP2011111678A JP2011111678A JP2010112653A JP2010112653A JP2011111678A JP 2011111678 A JP2011111678 A JP 2011111678A JP 2010112653 A JP2010112653 A JP 2010112653A JP 2010112653 A JP2010112653 A JP 2010112653A JP 2011111678 A JP2011111678 A JP 2011111678A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 70
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011777 magnesium Substances 0.000 title claims abstract description 52
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000007739 conversion coating Methods 0.000 title claims abstract description 14
- 238000011282 treatment Methods 0.000 claims abstract description 33
- 238000005238 degreasing Methods 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 52
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000080 wetting agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 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 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000009499 grossing Methods 0.000 claims description 2
- 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 2
- 239000000176 sodium gluconate Substances 0.000 claims description 2
- 235000012207 sodium gluconate Nutrition 0.000 claims description 2
- 229940005574 sodium gluconate Drugs 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 29
- 239000002184 metal Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 9
- 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
- 238000004381 surface treatment Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000003929 acidic solution Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 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
- 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
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002994 raw material Substances 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
- 239000002253 acid 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
- 230000007423 decrease Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000007689 inspection Methods 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
- 238000010422 painting Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- -1 rare earth salt Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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
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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
- C23C22/78—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)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (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
本発明は、マグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法に関するものであり、より詳しくは、マグネシウム又はマグネシウム合金の外面に環境親和的で、且つ高い耐食性を付与できる化成皮膜層を形成する方法に関するものである。 The present invention relates to a method for forming a chemical conversion film layer on the outer surface of magnesium or a magnesium alloy, and more specifically, forms a chemical conversion film layer that is environmentally friendly and can impart high corrosion resistance to the outer surface of magnesium or a magnesium alloy. It is about how to do.
一般的に、マグネシウムは地球上に豊富なだけでなく、密度が約１．７４ｇ／ｃｍ３であり、構造用金属材料中最も軽量なため、航空機、自動車および携帯用機器等に使用されており、使用量および適用範囲が急激に増加している。 In general, magnesium is not only abundant on the earth, but also has a density of about 1.74 g / cm 3 and is the lightest structural metal material, so it is used in aircraft, automobiles and portable equipment. The usage and application range are increasing rapidly.
しかし、マグネシウム合金は材質の特性上、耐食性に劣るという短所あるため、表面に化学処理を必須的に行わなければならなく、このような化学処理中で最も多く用いられて来た方法の一つに、化成皮膜形成後に塗装で仕上げる工程がある。 However, because magnesium alloys have the disadvantage of poor corrosion resistance due to the characteristics of the material, the surface must be chemically treated, which is one of the most widely used methods in such chemical treatment. In addition, there is a process of finishing by painting after forming the chemical conversion film.
化成皮膜形成方法は、マグネシウム表面に多様な化学反応によって皮膜が形成される金属表面処理の一つであり、皮膜の厚さは数百ｎｍ範囲を表し、化成処理溶液によって様々な種類がある。また、化成皮膜形成方法は外部から電気を加える電気メッキとは異なり、外部から電気を加えず、金属表面で起こる化学反応を利用して皮膜を得るという特徴がある。 The chemical conversion film forming method is one of metal surface treatments in which a film is formed on the magnesium surface by various chemical reactions. The thickness of the film represents a range of several hundred nm, and there are various types depending on the chemical conversion solution. Further, the chemical film forming method is characterized in that, unlike electroplating in which electricity is applied from the outside, no film is applied from the outside, and a film is obtained by utilizing a chemical reaction occurring on the metal surface.
このようなマグネシウム合金の化成皮膜形成方法は、一般的にクロム系化成処理と非クロム系化成処理方法がある。 Such a magnesium alloy chemical conversion film forming method generally includes a chromium-based chemical conversion treatment and a non-chromium chemical conversion treatment method.
クロム系化成処理は、７０年代にＤｏｗ Ｃｈｅｍｉｃａｌで開発され、Ｄｏｗ１やＤｏｗ２１のように命名され利用されている。代表的なＤｏｗ法は、重クロム酸ソーダを主成分として酸性溶液で金属表面処理が行われる。Ｄｏｗ法で使用される酸性溶液は、管理が容易で且つ表面処理後に金属の耐食性および塗装密着性がよいという長所がある。しかし、使用される酸性溶液内の６価クロムの有害性が見つかったため使用に制限がある。 The chromium-based chemical conversion treatment was developed by Dow Chemical in the 1970s, and is named and used as Dow1 or Dow21. In a typical Dow method, metal surface treatment is performed with an acidic solution containing sodium dichromate as a main component. The acidic solution used in the Dow method has advantages that it is easy to manage and has good metal corrosion resistance and coating adhesion after the surface treatment. However, the use of hexavalent chromium in the acidic solution to be used is limited because it has been found harmful.
これにより、低クロム系あるいは非クロム系化成処理方法が開発され利用されているが、非クロム系化成処理法は主にマンガン塩系およびジルコニウム塩系があり、その他希土類塩系と有機系が知られているが、処理液が高価だったり管理が大変だという短所がある。 As a result, low-chromium or non-chromium chemical conversion treatment methods have been developed and used, but the non-chromium chemical conversion treatment methods mainly include manganese salt and zirconium salt systems, and other rare earth salt and organic systems are known. However, it has the disadvantage that the processing solution is expensive and difficult to manage.
また、化成皮膜の色が、クロメートの場合は緑色や赤灰色を帯び、非クロム系の場合は灰色やアイボリー色を表すため、マグネシウムの金属の色がそのまま表現されないことから、マグネシウム合金外観の良さが低下する。 In addition, the color of the conversion coating is green or red-gray in the case of chromate, and gray or ivory in the case of non-chromium, so the magnesium metal color is not expressed as it is, so the appearance of the magnesium alloy is good. Decreases.
本発明の目的の一つは、マグネシウム又はマグネシウム合金の外面に化成皮膜層を形成して耐食性を向上させる方法を提供することである。 One of the objects of the present invention is to provide a method for improving the corrosion resistance by forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy.
本発明の他の目的は、環境に優しいマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法を提供することである。 Another object of the present invention is to provide a method for forming a conversion coating layer on the outer surface of an environmentally friendly magnesium or magnesium alloy.
本発明の他の目的は、マグネシウム又はマグネシウム合金の外面に化成皮膜層を形成して表面処理後にも外観の損傷を最小化する方法を提供することである。 Another object of the present invention is to provide a method for forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy so as to minimize appearance damage even after the surface treatment.
本発明の他の目的は、マグネシウム又はマグネシウム合金の外面に化成皮膜層を形成して外観の良さを最大化できる方法を提供することである。 Another object of the present invention is to provide a method capable of maximizing the appearance by forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy.
本発明の一実施例によるマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法は、マグネシウム又はマグネシウム合金の外面に脱脂処理した後に水洗い処理する工程；前記マグネシウム又はマグネシウム合金の外面の酸化皮膜除去のためのエッチング処理後に水洗い処理する工程；前記マグネシウム又はマグネシウム合金の外面に発生したスマット（ｓｍｕｔ）を除去するためのデスマット処理後に水洗い処理する工程；前記マグネシウム又はマグネシウム合金の外面に化成皮膜形成処理した後に水洗い処理する工程；及び前記化成皮膜上に塗装処理をする工程；を含む。 According to one embodiment of the present invention, a method for forming a chemical conversion film layer on the outer surface of magnesium or a magnesium alloy includes a step of degreasing the outer surface of the magnesium or magnesium alloy and then washing with water; removing the oxide film on the outer surface of the magnesium or magnesium alloy A step of washing with water after the etching treatment; a step of washing with water after desmutting to remove smut generated on the outer surface of the magnesium or magnesium alloy; and a chemical film forming treatment on the outer surface of the magnesium or magnesium alloy And a step of performing a washing treatment on the chemical conversion film.
前記のような方法によって耐食性が向上し、表面処理後にも外観の損傷を最小化し、見た目の良さを最大化できるマグネシウム又はマグネシウム合金が提供できる。 By such a method, it is possible to provide magnesium or a magnesium alloy that can improve corrosion resistance, minimize damage of appearance even after surface treatment, and maximize appearance.
前記マグネシウム又はマグネシウム合金の外面に脱脂処理した後に水洗い処理する工程で、前記脱脂処理は３０〜６０ｇ／Ｌの水酸化カリウム（ＫＯＨ）、１５０〜２００ｇ／Ｌの水酸化ナトリウム（ＮａＯＨ）、２０〜３０ｇ／Ｌのアミンオキシド、５〜１０ｇ／ＬのＣ６Ｈ１１ＮａＯ７（グルコン酸ナトリウム）及び浸潤剤（Ｗｅｔｔｉｎｇ ａｇｅｎｔ）で組成された第１水溶液によって処理できる。前記のように構成された第１水溶液は、マグネシウム又はマグネシウム合金表面の油成分を容易に除去でき、素材の変色を最小化できる。 In the step of degreasing the outer surface of the magnesium or magnesium alloy and washing with water, the degreasing treatment includes 30 to 60 g / L potassium hydroxide (KOH), 150 to 200 g / L sodium hydroxide (NaOH), 20 to 20 g. It can be treated with a first aqueous solution composed of 30 g / L of amine oxide, 5-10 g / L of C 6 H 11 NaO 7 (sodium gluconate) and a wetting agent. The 1st aqueous solution comprised as mentioned above can remove easily the oil component on the surface of magnesium or a magnesium alloy, and can minimize discoloration of a raw material.
前記マグネシウム又はマグネシウム合金の外面における酸化皮膜除去のためのエッチング処理後に水洗い処理する工程で前記エッチング処理は６００〜８００ｇ／Ｌの硝酸（ＨＮＯ３）、２００〜４００ｇ／Ｌの燐酸（Ｈ３ＰＯ４）及び浸潤剤を混合した第２水溶液によって処理できる。一方、第２水溶液は蒸留水で希釈してｐＨ１．０〜２．０に調整でき、約３５〜５０℃の温度範囲内で形成できる。前記のように構成された第２水溶液によって、マグネシウム又はマグネシウム合金表面の酸化膜が容易に除去でき、金属の変色を最小化できる。 In the step of washing with water after the etching process for removing the oxide film on the outer surface of the magnesium or magnesium alloy, the etching process includes 600 to 800 g / L nitric acid (HNO 3 ), 200 to 400 g / L phosphoric acid (H 3 PO 4 ) And a second aqueous solution mixed with an infiltrant. On the other hand, the second aqueous solution can be adjusted to pH 1.0-2.0 by diluting with distilled water, and can be formed within a temperature range of about 35-50 ° C. With the second aqueous solution configured as described above, the oxide film on the surface of magnesium or magnesium alloy can be easily removed, and the discoloration of the metal can be minimized.
一方、前記マグネシウム又はマグネシウム合金の外面に発生したスマットを除去するためのデスマット処理後に水洗い処理する工程で、前記デスマット処理は５０〜２００ｇ／Ｌの水酸化カリウム（ＫＯＨ）及び５〜１０ｇ／Ｌの平滑剤を混合した第３水溶液に浸漬処理できる。前記のような組成比率によって金属表面に水酸化皮膜の発生を防止でき、金属がデスマットされることを防止できる。 On the other hand, in the step of washing with water after desmutting treatment for removing smut generated on the outer surface of the magnesium or magnesium alloy, the desmutting treatment comprises 50 to 200 g / L potassium hydroxide (KOH) and 5 to 10 g / L. It can be dipped in a third aqueous solution mixed with a smoothing agent. The composition ratio as described above can prevent the formation of a hydroxide film on the metal surface and prevent the metal from being desmutted.
また、前記マグネシウム又はマグネシウム合金の外面に化成皮膜形成処理した後に水洗い処理する工程で、前記化成皮膜形成処理は６００〜８００ｇ／Ｌの硝酸（ＨＮＯ３）、２００〜４００ｇ／Ｌの燐酸（Ｈ３ＰＯ４）及び０．５〜１０ｇ／Ｌのフッ酸（ＨＦ）を混合した第４水溶液に処理できる。このとき、第４水溶液は蒸留水で希釈してｐＨ２．０〜４．０に調整して、２０〜６０℃の前記第４水溶液中で前記化成皮膜を形成できる。このように、第４水溶液の温度を限定することにより、皮膜形成速度を調節して金属表面に一定の厚さの皮膜が形成できるようにし、金属外観の損傷を最小化できる。 Further, in the step of subjecting the outer surface of the magnesium or magnesium alloy to a chemical film formation treatment and a water washing treatment, the chemical film formation treatment includes 600 to 800 g / L nitric acid (HNO 3 ), 200 to 400 g / L phosphoric acid (H 3 A fourth aqueous solution in which PO 4 ) and 0.5 to 10 g / L hydrofluoric acid (HF) are mixed can be treated. At this time, the fourth aqueous solution can be diluted with distilled water to adjust the pH to 2.0 to 4.0, and the chemical conversion film can be formed in the fourth aqueous solution at 20 to 60 ° C. Thus, by limiting the temperature of the fourth aqueous solution, the film formation rate can be adjusted so that a film with a certain thickness can be formed on the metal surface, and damage to the metal appearance can be minimized.
本発明の一実施例のマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法によると、酸アルカリとの反応性に優れ、活性が強いため耐食性が向上し得る。 According to the method of forming a chemical conversion film layer on the outer surface of magnesium or magnesium alloy according to one embodiment of the present invention, the corrosion resistance can be improved because of excellent reactivity with acid alkali and strong activity.
本発明の一実施例のマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法によると、クロム酸等の環境に有害な物質を使用せず、金属表面に皮膜を形成するため環境に優しい皮膜層を形成できる。
本発明の一実施例のマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法によると、マグネシウム又はマグネシウム合金の外面に表面処理をした後にもマグネシウムそのままの色を表現できるようになる。
According to the method of forming a chemical film on the outer surface of magnesium or a magnesium alloy according to an embodiment of the present invention, an environmentally friendly film is formed because a film is formed on the metal surface without using an environmentally harmful substance such as chromic acid. Layers can be formed.
According to the method of forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy according to one embodiment of the present invention, the color of magnesium as it is can be expressed even after the surface treatment is performed on the outer surface of the magnesium or magnesium alloy.
以下で、本発明にかかる実施例を添付の図面を参照して詳しく説明する。しかし、本発明が実施例によって制限されたり限定されるものではない。各図面に提示された同一な参照符号は同一な部材を表す。 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 examples. The same reference numerals provided in the drawings represent the same members.
図1は、本発明の一実施例にかかるマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法によって表面処理されたマグネシウム合金板材の表面組織の拡大図であり、図２は本発明の一実施例にかかるマグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法を図示した順序図である。 FIG. 1 is an enlarged view of a surface structure of a magnesium alloy sheet surface-treated by a method for forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy according to an embodiment of the present invention. FIG. It is the flowchart which showed the method of forming the chemical conversion film layer in the outer surface of the magnesium or magnesium alloy concerning an Example.
以下、図面を説明するためにマグネシウム合金表面に化成皮膜層を形成する例を挙げて説明するが、発明で要求される条件に従いマグネシウム金属板表面上に化成皮膜層が形成される場合もある。 Hereinafter, an example in which a chemical conversion film layer is formed on the surface of a magnesium alloy will be described for explaining the drawings. However, the chemical conversion film layer may be formed on the surface of the magnesium metal plate in accordance with the conditions required in the invention.
図面および［表１］を参考すると、成形したマグネシウム合金表面に付着している油脂成分と異物質を除去し、金属の変色を防止するためにマグネシウム合金表面を脱脂処理できる第１水溶液を形成できる（Ｓ２１０）。 Referring to the drawings and [Table 1], a first aqueous solution capable of removing the oil components and foreign substances adhering to the molded magnesium alloy surface and degreasing the magnesium alloy surface to prevent discoloration of the metal can be formed. (S210).
前記第１水溶液に提供された添加剤は浸潤剤であり、金属表面に第１水溶液をよく染み込むようにさせる界面活性剤になり得る。前記の界面活性剤は、発明で要求される条件に従い多様な浸潤剤が使用できる。 The additive provided to the first aqueous solution is a wetting agent and can be a surfactant that causes the first aqueous solution to penetrate well into the metal surface. Various surfactants can be used as the surfactant according to the conditions required in the invention.
このとき、第１水溶液の組成比率を提示した［表１］の範囲から外れると、マグネシウム合金表面の油成分が除去される速度が遅くなったり金属の素材が変色し得るため、第１水溶液の組成比率は図示の範囲内であることが好ましい。 At this time, if the composition ratio of the first aqueous solution is out of the range of [Table 1], the rate at which the oil component on the surface of the magnesium alloy is removed may be slow or the metal material may be discolored. The composition ratio is preferably within the range shown in the figure.
前記第１水溶液を利用してマグネシウム合金表面の油脂成分と異物質を除去した後、水洗い処理できる（Ｓ２１０）。前記水洗い処理でマグネシウム合金表面に残っている第１水溶液成分を完全に除去できる。 After removing the fat and oil components and foreign substances on the surface of the magnesium alloy using the first aqueous solution, it can be washed with water (S210). The first aqueous solution component remaining on the surface of the magnesium alloy can be completely removed by the washing treatment.
第１水溶液は、強アルカリ成分であるため、もしマグネシウム合金表面に第１水溶液成分が残っていると、後工程で使用される強酸性溶液と反応して金属表面の化学的な反応を低下させ、金属表面が不均衡に形成され得る。よって、水洗い処理を通じて金属表面に残っている第１水溶液を完全に除去することで後工程の効率を向上させることができる。 Since the first aqueous solution is a strong alkali component, if the first aqueous solution component remains on the surface of the magnesium alloy, it reacts with the strongly acidic solution used in the subsequent step to reduce the chemical reaction on the metal surface. , The metal surface can be formed disproportionately. Therefore, the efficiency of the post-process can be improved by completely removing the first aqueous solution remaining on the metal surface through the water washing treatment.
脱脂処理が終了すると、金属表面のマグネシウム酸化皮膜を除去するために［表２］のような第２水溶液を製造できる（Ｓ２２０）。 When the degreasing treatment is completed, a second aqueous solution as shown in [Table 2] can be manufactured to remove the magnesium oxide film on the metal surface (S220).
前記第２水溶液に提供された浸潤剤は前述の説明通り金属に溶液をよく染み込むようにさせた界面活性剤であって、発明で要求される条件に従い多様に提供できる。 The infiltrant provided in the second aqueous solution is a surfactant that allows the solution to soak into the metal as described above, and can be provided in various ways according to the conditions required in the invention.
前記第２水溶液を利用してマグネシウム合金表面をエッチング処理すると、金属表面の酸化皮膜を適切な速度で除去でき、金属の変色を防止できる。 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 rate, and discoloration of the metal can be prevented.
マグネシウム合金のエッチング処理が終了すると、水洗い処理ができる（Ｓ２２０）。前述の説明通り水洗い処理は金属表面の酸化皮膜を除去する過程で使用される溶液が工程後に表面に残って金属の外観の損傷を防止できる。 When the magnesium alloy etching process is completed, a water washing process can be performed (S220). As described above, the washing treatment can prevent damage to the appearance of the metal because the solution used in the process of removing the oxide film on the metal surface remains on the surface after the process.
エッチング処理および水洗い処理が終了すると、［表３］のように第３水溶液を製造してマグネシウム合金表面に発生したスマットを除去できる（Ｓ２３０）。 When the etching process and the water washing process are completed, the third aqueous solution is manufactured as shown in [Table 3], and the smut generated on the surface of the magnesium alloy can be removed (S230).
前記 [表３]に図示した組成比率で製造された第３水溶液はデスマット溶液であって、金属表面のムラ等を除去でき、添加剤である平滑剤を添加して金属表面を平らにできる。 The third aqueous solution produced in the composition ratio shown in Table 3 is a desmut solution, which can remove unevenness on the metal surface and can add a leveling agent as an additive to flatten the metal surface.
また、第３水溶液は、前記［表３］の組成比率に従って調製されることが好ましい。もし第３水溶液が前記組成比率より低い場合は金属表面の一部のみデスマット処理され、組成比率より高い場合は金属表面に水酸化皮膜が形成できる。よって、第３水溶液の組成比率は前記範囲から外れないことが好ましい。 The third aqueous solution is preferably prepared according to the composition ratio of [Table 3]. If the third aqueous solution is lower than the composition ratio, only a part of the metal surface is desmutted. If the third aqueous solution is higher than the composition ratio, a hydroxide film can be formed on the metal surface. Therefore, it is preferable that the composition ratio of the third aqueous solution does not deviate from the above range.
一方、マグネシウム合金表面に発生したスマットが除去されると、マグネシウム合金を水洗い処理した後（Ｓ２３０）で、マグネシウム合金の外面に化成皮膜を形成できる（Ｓ２４０）。マグネシウム合金の外面に化成皮膜を形成するために第４水溶液を製造でき、第４水溶液の組成比率は次の通りである。 On the other hand, when the smut generated on the surface of the magnesium alloy is removed, a chemical conversion film can be formed on the outer surface of the magnesium alloy (S240) after the magnesium alloy is washed with water (S230). A fourth aqueous solution can be produced 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.
前記の通り製造された第４水溶液によってマグネシウム合金上に形成された化成皮膜上に塗装処理できる（Ｓ２５０）。 The chemical conversion film formed on the magnesium alloy can be coated with the fourth aqueous solution manufactured as described above (S250).
前記塗装処理後に金属の耐食性検査のための塩水噴霧試験で３６時間後の結果と、皮膜と金属間の密着性試験を行った結果を次の通り表した。 The results after 36 hours in the salt spray test for the corrosion resistance inspection of the metal after the coating treatment and the results of the adhesion test between the film and the metal are shown as follows.
前記のような化成皮膜を形成する方法によって形成されたマグネシウム合金の表面は、マグネシウムそのままの金属色を維持でき、金属表面の損傷を最小化できる。また、マグネシウム合金の耐食性を向上させて多様な機器の原料として使用できる。さらに、既存のクロメート、クロム酸等のような毒性の強い化成皮膜を使用しないため、環境に優しい皮膜層を形成することもできる。 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, and can minimize damage to the metal surface. Further, the corrosion resistance of the magnesium alloy can be improved and used as a raw material for various devices. Furthermore, since a highly toxic chemical conversion film such as existing chromate and chromic acid is not used, an environmentally friendly film layer can be formed.
以上では、本発明の好ましい実施例を例示的に説明したが、本発明の範囲はこのような特定実施例だけに限定されるものではなく、特許請求の範囲に記載されている範疇内で適切に変更できる。 In the above, the preferred embodiments of the present invention have been described by way of example, but the scope of the present invention is not limited to such specific embodiments, and appropriate within the scope described in the claims. Can be changed.
Claims (7)
マグネシウム又はマグネシウム合金の外面に脱脂処理した後に水洗い処理する工程；
前記マグネシウム又はマグネシウム合金の外面の酸化皮膜除去のためのエッチング処理後に水洗い処理する工程；
前記マグネシウム又はマグネシウム合金の外面に発生したスマットを除去するためのデスマット処理後に水洗い処理する工程；
前記マグネシウム又はマグネシウム合金の外面に化成皮膜形成処理した後に水洗い処理する工程；及び
前記化成皮膜上に塗装処理する工程；
を含むことを特徴とする、マグネシウム又はマグネシウム合金の外面に化成皮膜層を形成する方法。 In the method of forming a chemical conversion film layer on the outer surface of magnesium or a magnesium alloy,
Degreasing the outer surface of magnesium or magnesium alloy and then washing with water;
Washing with water after the etching treatment for removing the oxide film on the outer surface of the magnesium or magnesium alloy;
A step of washing with water after desmutting treatment for removing smut generated on the outer surface of the magnesium or magnesium alloy;
A step of subjecting the outer surface of the magnesium or magnesium alloy to a chemical film formation treatment and then a water washing treatment; and a coating treatment on the chemical conversion film;
A method of forming a chemical conversion coating layer on the outer surface of magnesium or a magnesium alloy, comprising:
The fourth aqueous solution is diluted with distilled water to adjust the pH to 2.0 to 4.0, and the chemical conversion film is formed in the fourth aqueous solution at 20 to 60 ° C. 6. A method for forming a chemical conversion film layer on the outer surface of magnesium or magnesium alloy according to 6.
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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 |
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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 |
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