KR100293237B1 - Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same - Google Patents
Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same Download PDFInfo
- Publication number
- KR100293237B1 KR100293237B1 KR1019960069477A KR19960069477A KR100293237B1 KR 100293237 B1 KR100293237 B1 KR 100293237B1 KR 1019960069477 A KR1019960069477 A KR 1019960069477A KR 19960069477 A KR19960069477 A KR 19960069477A KR 100293237 B1 KR100293237 B1 KR 100293237B1
- Authority
- KR
- South Korea
- Prior art keywords
- plating
- mol
- electro
- steel sheet
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 17
- 239000011701 zinc Substances 0.000 title claims abstract description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 5
- 239000008397 galvanized steel Substances 0.000 title claims description 5
- 238000007747 plating Methods 0.000 claims abstract description 81
- 239000007788 liquid Substances 0.000 claims abstract description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009713 electroplating Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 14
- 239000010959 steel Substances 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 sulfone compound Chemical class 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
본 발명은 전기아연도금용액 및 이를 이용한 전기아연도금강판의 제조방법에 관한 것이며, 그 목적은 표면외관 균일성이 우수한 전기아연도금용액 및 이를 이용한 전기아연도금강판을 제공함에 있다.The present invention relates to an electrogalvanized solution and a method for producing an electrogalvanized steel sheet using the same, and an object thereof is to provide an electrogalvanized solution having excellent surface appearance uniformity and an electrogalvanized steel sheet using the same.
상기 목적을 달성하기 위한 본 발명은 염화물계 전기아연도금용액에 있어서, 아연 이온농도가 0.5-2.3몰/ℓ, Cl-이온농도가 2.0-11.3몰/ℓ를 기본으로 하고, 여기에 마그네슘의 이온농도가 0.005-1.0몰/ℓ로 함유하여 구성되는 표면외관 균일성이 우수한 전기아연도금용액과 상기 도금액의 pH를 2.0-6.0의 범위로 조절하고, 상기 도금액의 온도를 40-70℃의 범위로 유지한 다음, 전류밀도를 20-250A/dm2, 상대유속을 0.5-3.0m/sec의 조건으로 하여 전기도금하여 구성되는 표면외관 균일성이 우수한 전기아연도금강판 제조방법에 관한 것을 그 요지로 한다.The present invention for achieving the above object is based on the zinc-based electro zinc plating solution, the zinc ion concentration is 0.5-2.3 mol / l, Cl - ion concentration is based on 2.0-11.3 mol / l, where magnesium ions The pH of the electrolytic zinc plating solution and the plating liquid having excellent surface appearance uniformity, containing the concentration of 0.005-1.0 mol / l, in the range of 2.0-6.0, and the temperature of the plating liquid in the range of 40-70 ° C. The present invention relates to a method for producing an electro-zinc plated steel sheet having excellent surface appearance uniformity, which is formed by electroplating under the condition of a current density of 20-250 A / dm 2 and a relative flow rate of 0.5-3.0 m / sec. do.
Description
본 발명은 전기아연도금용액 및 이를 이용한 전기아연도금 강판의 제조방법에 관한 것으로서, 보다 상세하게는, 염화물계 도금용액에 마그네슘 이온을 첨가하여 도금층의 표면외관 및 균일성이 우수한 전기아연 도금용액 및 이를 이용한 전기아연도금강판을 제조하는 방법에 관한 것이다.The present invention relates to an electrogalvanized solution and a method for producing an electrogalvanized steel sheet using the same. More specifically, an electrozinc plating solution having excellent surface appearance and uniformity by adding magnesium ions to a chloride-based plating solution, and It relates to a method of manufacturing an electrogalvanized steel sheet using the same.
일반적으로 강판의 방청성을 확보하기 위한 방법으로서 아연도금이 널리 사용되고 있으며, 특히 전기아연도금은 용융아연도금에 비해 도금부착량 조절이 용이하고 박 도금이 가능하며 아연도금층의 표면외관이 양호하다. 그러므로 도장처리용에서부터 수요가의 요구에 따라 인산염처리 또는 크로메이트처리 및 유기수지를 도포처리하여 내식성, 내지문성 또는 윤활성 등의 기능을 부여함으로써, 가전, 자동차, 건축자재 둥에 폭넓게 사용되고 있다.In general, zinc plating is widely used as a method for securing the rust resistance of steel sheets, and in particular, electrogalvanization is easier to control the coating amount than the hot dip galvanizing, thin plating is possible, and the surface appearance of the zinc plating layer is good. Therefore, it is widely used in home appliances, automobiles, and building materials by providing functions such as corrosion resistance, fingerprint resistance, or lubricity by applying phosphate treatment, chromate treatment, and organic resin coating according to demands of paint processing.
이와 같은 전기아연도금강판에서 아연도금층의 표면외관 및 균일성이 불량할 경우, 여러 가지 후처리 공정(인산염처리, 크로메이트처리, 내지문 또는 윤활수지피복처리)을 거친다 하더라도 전기도금층의 불량이 그대로 나타나게 되어 표면불량이 선명해질 뿐만 아니라, 일부는 도장(분체도장 또는 전착도장) 외관 및 선영성에 좋지 않은 영향을 미치게 된다. 따라서, 전기아연도금강판을 상기와 같은 용도로 사용하기 위해서는 아연 도금층의 표면물성 즉, 표면외관의 균일성 및 백색도와 광택도가 우수해야 한다.If the surface appearance and uniformity of the zinc plated layer is poor in such an electrogalvanized steel sheet, even if it undergoes various post-treatment processes (phosphate treatment, chromate treatment, rubbing or lubrication resin coating treatment), the defect of the electroplating layer will remain as it is. Not only the surface defects become clear, but some of them have a bad effect on the appearance and powderiness of the coating (powder coating or electrodeposition coating). Therefore, in order to use the electro-galvanized steel sheet for the above purposes, the surface properties of the galvanized layer, that is, the uniformity of the surface appearance and the whiteness and gloss should be excellent.
상기와 같이 표면외관이 우수한 전기아연도금강판을 제조하기 위해서는 전기아연도금의 작업조건을 최적으로 관리하면서 도금을 실시해야만 하며, 도금액 중에 유기물 또는 무기물 첨가제를 첨가시키는 방법이 효과적인 것으로 알려지고 있다.In order to manufacture an electrogalvanized steel sheet having excellent surface appearance as described above, plating should be performed while optimally managing the working conditions of electrogalvanizing, and it is known that a method of adding an organic or inorganic additive to a plating solution is effective.
종래, 염화물계 도금액의 경우 (1) 일본 특허공개 공보(소)42-8764호에서의 폴리에틸렌 옥사이드 알킬레이트 슬폰 화합물을 첨가하는 방법과 (2) 일본 특허공개 공보(소)58-26438호에서의 NH4Cl, KCl, NaCl, AlCl3, BaCl2, CaCl2, FeCl2, FeCl3, MgCl2및 MnCl2중 적어도 1가지 이상을 100-400g/l 함유하는 도금액에서 도금하는 방법등이 있다. 그러나 이러한 방법(1)은 아연 도금층의 광택을 개선시키는 효과가 있으나 도금액에서의 농도관리 및 분석이 어려우므로 품질편차를 발생할 우려가 있다. 또한 방법 (2)에서는, 도금액 중의 전도보조제로서 여러 가지 염화물을 사용할 수 있으나, 일부 금속염의 경우 도금층에 공석되어 오히려 불순물로 작용하거나 과량의 무기금속 첨가에 의해 도금층 표면외관이 열화되는 문제점이 있다.Conventionally, in the case of a chloride plating solution, (1) a method of adding a polyethylene oxide alkylate sulfone compound in Japanese Patent Application Laid-Open No. 42-8764 and (2) Japanese Patent Laid-Open Publication No. 58-26438 And at least one of NH 4 Cl, KCl, NaCl, AlCl 3 , BaCl 2 , CaCl 2 , FeCl 2 , FeCl 3 , MgCl 2 and MnCl 2 in a plating solution containing 100-400 g / l. However, this method (1) has an effect of improving the gloss of the galvanized layer, but there is a concern that quality deviation may occur because concentration control and analysis in the plating solution are difficult. In addition, in the method (2), various chlorides may be used as the conductive assistant in the plating solution, but some metal salts are vaccinated in the plating layer, and thus act as impurities or deteriorate the surface appearance of the plating layer by the addition of excess inorganic metal.
따라서, 본 발명은 상기 종래 문제를 해결하기 위하여 제안된 것으로서, 염화물계 도금액중에 마그네슘 이온을 적정량 첨가함으로써, 넓은 전해조건에서 전기 아연도금층의 표면외관을 미려하고 균일하게 하며, 표면의 백색도와 광택도가 우수한 전기아연도금용액 및 이를 이용한 전기아연도금강판의 제조방법을 제공하는데, 그 목적이 있다.Therefore, the present invention has been proposed to solve the above-mentioned conventional problems, by adding an appropriate amount of magnesium ions in the chloride-based plating solution, to make the surface appearance of the electrogalvanized layer in a wide electrolytic condition, to make the surface appearance of the electrolytic galvanized layer uniform and uniform, the surface whiteness and glossiness To provide an excellent electrogalvanized solution and a method for producing an electrogalvanized steel sheet using the same, the purpose is.
상기 목적을 달성하기 위한 본 발명의 일측면은, 염화물계 전기아연도금용액에 있어서, 아연이온농도가 0.5-2.3몰/ℓ, Cl-이온농도가 2.0-11.3몰/ℓ를 기본으로 하고, 여기에 마그네슘의 이온농도가 0.005-1.0몰/ℓ로 함유되어 구성되는 표면외관 균일성이 우수한 전기아연도금강판을 제조하기 위한 전기아연도금용액에 관한 것이다.One aspect of the present invention for achieving the above object, in the chloride-based electro zinc plating solution, the zinc ion concentration is 0.5-2.3 mol / l, Cl - ion concentration is based on 2.0-11.3 mol / l, The present invention relates to an electrogalvanized solution for producing an electrogalvanized steel sheet having excellent surface appearance uniformity, wherein the magnesium has an ion concentration of 0.005-1.0 mol / l.
또한, 본 발명의 다른 측면은 전기아연도금강판의 제조방법에 있어서,In addition, another aspect of the present invention is a method for producing an electrogalvanized steel sheet,
아연이온농도 : 0.5-2.3몰/ℓ, Cl-이온농도 : 2.0-11.3몰/ℓ, 마그네슘이온농도 : 0.005-1.0몰/ℓ, 로 조성되는 도금액의 pH를 2.0-6.0의 범위로 조절하고, 상기 도금액의 온도를 40-70℃의 범위로 유지한 다음, 전류밀도를 20-250A/dm2, 상대유속을 0.5-3.0m/sec의 조건으로 하여 전기도금하여 구성되는 표면외관 균일성이 우수한 전기아연도금강판 제조방법에 관한 것이다.Zinc ion concentration: 0.5-2.3 mol / l, Cl - ion concentration: 2.0-11.3 mol / l, magnesium ion concentration: 0.005-1.0 mol / l, the pH of the plating solution is adjusted to the range of 2.0-6.0, After maintaining the temperature of the plating solution in the range of 40-70 ℃, excellent surface appearance uniformity formed by electroplating at a current density of 20-250A / dm 2 and a relative flow rate of 0.5-3.0m / sec It relates to a method for producing an electrogalvanized steel sheet.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따라 전기아연도금을 실시하는 경우, 도금액의 아연이온농도가 0.5몰/ℓ 이하인 경우에는 아연이온의 농도부족에 의해서 도금전압이 증가되며 도금층 조직이 커져 표면이 검게되는 탄도금(burning)을 일으키고, 2.3몰/ℓ 이상에서는 분말상태의 도금층이 나타나 도금밀착성이 떨어지기 때문에 아연이온농도는 0.5-2.3몰/ℓ로 유지하는 것이 바람직하다.In the case of conducting electro-galvanization according to the present invention, when the zinc ion concentration of the plating solution is 0.5 mol / l or less, the plating voltage is increased due to the lack of concentration of zinc ions, and the surface of the plating layer grows to blacken the surface (burning). It is preferable to maintain the zinc ion concentration at 0.5-2.3 mol / l because at least 2.3 mol / l, a powder-plated layer appears and plating adhesion is inferior.
또한, 도금액의 Cl-이온농도가 2.0몰/ℓ 이하의 경우 도금액의 전기전도도 감소로 인하여 탄도금이 발생할 우려가 있고, 11.3몰/ℓ 이상의 경우 도금액에서의 용해도 문제로 염화이온이 석출되어 도금작업성 및 도금액 농도관리에 문제점을 초래하고 이에 따라 도금품질이 저하되므로, 염화이온농도는 2.0-11.3몰/ℓ로 조절하는 것이 바람직하다.In addition, when the Cl - ion concentration of the plating liquid is 2.0 mol / l or less, there is a possibility that ballistic plating may occur due to the decrease in the electrical conductivity of the plating liquid, and in the case of 11.3 mol / l or more, the chloride ion is precipitated due to the solubility problem in the plating liquid. Chloride ion concentration is preferably adjusted to 2.0-11.3 mol / l, because it causes problems in the control of the coating and plating solution concentration and thereby deteriorates the plating quality.
그리고, 도금액중의 마그네슘 이온농도가 0.005몰/ℓ(Mg 0.122g/l)이하의 경우 마그네슘의 첨가효과가 미약하여 고농도 염소이온에서 아연 도금층의 백색도 값이 저하될 뿐만 아니라 도금줄무니 발생이 심해질 우려가 있고, 1.0몰/ℓ(Mg 24.3g/l) 이상의 경우 마그네슘의 첨가에 의한 전기아연도금충의 표면외관 향상효과가 포화에 도달되어 도금층이 거칠어져 표면외관이 불량하게 되므로 도금액의 마그네슘 이온농도는 0.005-1.0몰/ℓ(Mg 0.122-24.3g/l)로 조절되는 것이 바람직하다.When the magnesium ion concentration in the plating liquid is less than 0.005 mol / l (Mg 0.122 g / l), the effect of magnesium addition is insignificant. In the case of 1.0 mol / l (Mg 24.3g / l) or more, the surface appearance improvement effect of the electro zinc plating insect by the addition of magnesium reaches saturation and the plating layer becomes rough, resulting in poor surface appearance. It is preferably adjusted to 0.005-1.0 mol / l (Mg 0.122-24.3 g / l).
이와 같은 마그네슘이온은 MgO 또는 MgCl2·6H2O 등의 화합물로 첨가하는 것이 보다 바람직하며, MgSO4, MgSO4·7H2O, Mg(NO3)2·6H2O 등의 황산염 및 질산염을 사용하는 것은 염화물계 도금액에의 황산이온 및 질산이온 혼입으로 바람직하지 않다.Such magnesium ions are more preferably added with a compound such as MgO or MgCl 2 · 6H 2 O, and sulfates and nitrates such as MgSO 4 , MgSO 4 · 7H 2 O, Mg (NO 3 ) 2 · 6H 2 O, and the like. It is not preferable to use sulfate ions and nitrates in the chloride plating solution.
상기와 같이 조성되는 도금액의 pH가 2.0 이하에서는 아연도금충 표면의 백색도가 낮고 광택이 저하되며 도금줄무늬 발생이 심하고, 6.0 이상에서는 도금액중 아연이온이 수산화이온과 결합하여 수산화아연을 만들게 되어 도금액 농도 변화가 심하고 침전물이 생겨 도금표면이 거칠어지므로 도금액의 pH는 2.0-6.0로 제한하는 것이 바람직하다.When the pH of the plating liquid is as described above, the whiteness of the surface of the galvanized larva is low, the gloss decreases, and the plating streaks are severe. In 6.0 or above, zinc ions in the plating liquid are combined with hydroxide ions to form zinc hydroxide, thereby forming a concentration of the plating liquid. It is preferable to limit the pH of the plating solution to 2.0-6.0 because the change is severe and deposits are roughened on the plating surface.
또한, 상기 도금액의 온도가 40℃ 이하의 경우 도금전압이 증가될 뿐만 아니라 아연도금층의 백색도 및 광택이 저하되며, 70℃ 이상의 경우 도금액 증발이 심하여 농도편차가 발생되고 공해 문제를 유발시키며 도금작업성이 열악하게 될 뿐만 아니라 도금줄무늬 발생이 증가되므로 도금액의 온도는 40-70℃로 제한하는 것이 바람직하다.In addition, when the temperature of the plating liquid is 40 ℃ or less, the plating voltage is not only increased, but also the whiteness and gloss of the zinc plating layer are lowered. If the plating liquid is more than 70 ℃, evaporation of the plating solution is severe, causing concentration deviation and causing pollution problems. It is preferable that the temperature of the plating liquid is limited to 40-70 ° C. because not only this becomes worse but also the occurrence of plating streaks is increased.
상기와 같이 조절된 도금액을 사용하여 전기아연도금하는 경우, 전류밀도가 20A/dm2이하이면 아연도금층이 거칠어지고 표면외관이 불균일할 뿐만 아니라 낮은 전류밀도 조업으로 생산성이 떨어지며, 전류밀도가 25OA/dm2이상의 경우 한계전류밀도 범위를 넘게 되어 도금표면이 검게되고 도금층 결정립이 크게 나타나는 탄도금이 발생되어 정상적인 아연도금의 품질을 얻을 수 없으므로, 전류밀도는 20-250A/dm2로 제한하는 것이 바람직하다.In the case of electro-galvanizing using the plating liquid adjusted as described above, if the current density is 20A / dm 2 or less, the zinc plating layer becomes rough and the surface appearance is uneven, and the productivity decreases due to low current density operation, and the current density is 25OA / In the case of dm 2 or more, the current density should be limited to 20-250A / dm 2 because it exceeds the limit current density range, the plating surface becomes black and the ballistic plating which shows the plating layer grains is large, and thus the normal zinc plating quality cannot be obtained. Do.
본 발명에서 강판에 대한 도금액의 상대 이동속도를 나타내는 유속이 0.5m/sec 미만일 경우에는 저속작업에 따른 도금층 표면오염과 저전류밀도에 의해 도금표면이 거칠어지는 문제점이 있으며, 3.0m/sec 이상인 경우에는 상대유속 증가에 따른 도금액의 비산의 문제점이 예상되므로 강판에 대한 도금액의 상대유속은 0.5-3.0m/sec로 제한하는 것이 바람직하다.In the present invention, when the flow rate indicating the relative moving speed of the plating liquid relative to the steel sheet is less than 0.5 m / sec, there is a problem that the plating surface is roughened by the surface contamination and low current density due to the low speed operation, and when the flow rate is 3.0 m / sec or more. Since the problem of scattering of the plating liquid due to the increase in the relative flow rate is expected, the relative flow rate of the plating liquid on the steel sheet is preferably limited to 0.5-3.0 m / sec.
이하, 실시예를 통해 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
본 발명의 마그네슘이온 첨가에 따른 효과를 알아보기 위해, 두께 0.8㎜인 냉연강판을 전처리(알카리탈지, 산세)하고 염화물계 도금액인 하기 표1에 나타난 도금액 농도 및 도금조건으로 전기아연도금강판을 제조하였으며, 전기 아연도금층의 도금 부착량은 20g/㎡로 일정하게 하였다.In order to examine the effect of the magnesium ion of the present invention, pre-treated (alkaline degreasing, pickling) 0.8 mm thick cold rolled steel sheet and produced an electro-galvanized steel sheet with the plating solution concentration and plating conditions shown in Table 1 below the chloride-based plating solution. The plating adhesion of the electrogalvanized layer was kept constant at 20 g / m 2.
하기 표 1에 나타낸 전기아연도금층 표면의 백색도는 Color and Color Difference Meter C-5120(TOKYO DENSHOKU)에 의해 측정된 값(L*)이고, 광택도는 Gloss Meter(ERICHSEN)에 의해 입사각 60°로 측정하였고, 도금줄무늬는 육안관찰 하였으며, 각각의 평가는 하기와 같이 구분하여 나타내었다.The whiteness of the surface of the galvanized layer shown in Table 1 is a value (L *) measured by Color and Color Difference Meter C-5120 (TOKYO DENSHOKU), and the glossiness is measured at an incident angle of 60 ° by a Gloss Meter (ERICHSEN). The plating stripes were visually observed and each evaluation was shown as follows.
백색도 : ◎ 85이상, ○ 80-85, △ 75-80, × 75 이하Whiteness: ◎ 85 or more, ○ 80-85, △ 75-80, × 75 or less
광택도 : ◎ 20이상, ○ 10-20, △ 5-10, × 15이하Glossiness: ◎ 20 or more, ○ 10-20, △ 5-10, × 15 or less
도금줄무늬 : ◎ 없음, ○ 미소발생, △ 일부발생, × 전면에 다량발생Plating Stripe: ◎ None, ○ Small Occurrence, △ Partial Occurrence, × Large Amount on Front
[표 1]TABLE 1
상기 표1에 나타난 바와 같이, 본 발명의 제조방법대로 도금액에 마그네슘 이온을 0.005-1.0몰/ℓ로 부가하여 도금한 발명재(1-9)는, 도금액의 pH, 온도, 유속 및 전류밀도 등의 도금조건이 넓은 범위로 변화되어도 전기아연도금층의 백색도와 광택도가 높고 도금줄무늬 발생이 없이 표면외관이 우수하며 균일성이 유지되지만, 마그네슘이온이 첨가되지 않았거나 발명의 범위를 벗어난 도금용액 및 도금조건에서 실시된 비교재(1-8)에서는, 도금층의 백색도 및 광택도가 낮고 도금조건에 따른 도금층 표면외관 변화가 큰 것을 알 수 있었다.As shown in Table 1 above, the invention material (1-9) plated by adding magnesium ions to 0.005-1.0 mol / l in the plating solution according to the production method of the present invention, the pH, temperature, flow rate and current density of the plating solution, etc. Although the plating condition of the electroplating layer is changed to a wide range, the electrolytic galvanized layer has high whiteness and gloss, excellent surface appearance and uniformity without plating streaks, but no plating solution or magnesium ions added or beyond the scope of the invention. In Comparative Material 1-8 performed under the plating conditions, it was found that the whiteness and glossiness of the plating layer were low and the surface appearance change of the plating layer was large according to the plating conditions.
상술한 바와 같이, 본 발명은 염화물계 전기아연도금액에 있어서 유기첨가제를 첨가시키지 않고 마그네슘 이온농도를 0.005-1.0몰/ℓ 범위로 유지한 도금용액을 이용함으로써, 종래재와 비교하여 도금액중의 아연이온과 염화이온의 농도에 관계없이 다른 도금조건이 변화되어도 넓은 전해조건에서 아연도금층의 표면외관이 균일하여 백색도와 광택도가 양호하고, 도금줄무늬가 없는 표면의관이 우수한 전기아연도금 강판을 제공 할 수 있는 효과가 있다.As described above, the present invention utilizes a plating solution in which a magnesium ion concentration is maintained in the range of 0.005-1.0 mol / L without adding an organic additive in a chloride type electro zinc plating solution, and compared with the conventional material. Even if the plating conditions are different regardless of the concentration of zinc ions and chloride ions, the surface appearance of the zinc plated layer is uniform under wide electrolytic conditions. There is an effect that can be provided.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960069477A KR100293237B1 (en) | 1996-12-21 | 1996-12-21 | Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019960069477A KR100293237B1 (en) | 1996-12-21 | 1996-12-21 | Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR19980050640A KR19980050640A (en) | 1998-09-15 |
| KR100293237B1 true KR100293237B1 (en) | 2001-09-17 |
Family
ID=37527220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019960069477A Expired - Fee Related KR100293237B1 (en) | 1996-12-21 | 1996-12-21 | Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100293237B1 (en) |
-
1996
- 1996-12-21 KR KR1019960069477A patent/KR100293237B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR19980050640A (en) | 1998-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR890001107B1 (en) | Process for preparing zn - fe base alloy electroplated steel strips | |
| JP3233784B2 (en) | Electrogalvanized steel sheet with excellent appearance | |
| US4251329A (en) | Process for producing a highly corrosion resistant electroplated steel sheet | |
| EP0250792B1 (en) | A chromate treatment of a metal coated steel sheet | |
| KR930000469B1 (en) | Method of producing a steel sheet plated with zn-mg alloy and steel sheet plate with the same | |
| KR100293237B1 (en) | Manufacturing method of electro zinc plated solution with excellent surface appearance uniformity and electro galvanized steel sheet using same | |
| US20110287186A1 (en) | Method for making a phoshate-treated galvanized steel sheet | |
| KR100256427B1 (en) | Method of making znic electroplating with excellent surface | |
| KR0143502B1 (en) | Manufacturing method of zinc electric plated steel plate | |
| KR100349141B1 (en) | Method for manufacturing electro galvanized steel sheet with good appearance | |
| KR100419659B1 (en) | A plating solution for blackening zinc-nickel alloy coated steel sheet and electroplating method for zinc-nickel steel sheet | |
| KR100576043B1 (en) | Zinc-nickel alloy electroplating solution with good plating adhesion and gloss and suppressed carbon plating | |
| KR100403461B1 (en) | Electro zinc plating method of steel sheet | |
| JP2001040494A (en) | Electrogalvanized steel sheet excellent in surface appearance and its production | |
| KR100417615B1 (en) | Method for making Zn electrodeposit additive | |
| JPS6254099A (en) | Composite-plated steel sheet having superior spot welability and corrosion resistance and its manufacture | |
| JP7669992B2 (en) | Manufacturing method of electrolytic Zn-Ni alloy plated steel sheet | |
| KR100578214B1 (en) | Manufacturing method of zinc-magnesium electroplated steel sheet | |
| JPS62278297A (en) | Method for chromating metal-surface-treated steel sheet | |
| KR20020051276A (en) | Zn-Ni alloy electrolyte for good surface roughness, whiteness and suppression of edge burning and its electroplating process | |
| JPH0874089A (en) | Electrogalvanized steel sheet having excellent whiteness and method for producing the same | |
| JPH04124295A (en) | Production of thick galvanized steel sheet | |
| KR100373678B1 (en) | Additive of zinc-iron alloy electroplating solution | |
| KR960002637B1 (en) | Method for producing a steel sheet to treat blackening | |
| KR100368221B1 (en) | Electrolyte of zn-ni alloy electrodeposit in soluable anode and chroides bath and the method of manufacturing zn-ni alloy electric plating steel by using it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 19961221 |
|
| A201 | Request for examination | ||
| PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 19980729 Comment text: Request for Examination of Application Patent event code: PA02011R01I Patent event date: 19961221 Comment text: Patent Application |
|
| PG1501 | Laying open of application | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20000727 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20010226 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20010402 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 20010402 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| FPAY | Annual fee payment |
Payment date: 20040401 Year of fee payment: 4 |
|
| PR1001 | Payment of annual fee |
Payment date: 20040401 Start annual number: 4 End annual number: 4 |
|
| LAPS | Lapse due to unpaid annual fee | ||
| PC1903 | Unpaid annual fee |
Termination category: Default of registration fee Termination date: 20060410 |