KR100256427B1 - Method of making znic electroplating with excellent surface - Google Patents
Method of making znic electroplating with excellent surface Download PDFInfo
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- KR100256427B1 KR100256427B1 KR1019950059138A KR19950059138A KR100256427B1 KR 100256427 B1 KR100256427 B1 KR 100256427B1 KR 1019950059138 A KR1019950059138 A KR 1019950059138A KR 19950059138 A KR19950059138 A KR 19950059138A KR 100256427 B1 KR100256427 B1 KR 100256427B1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/02—Heating or cooling
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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Abstract
Description
본 발명은 표면외관이 우수한 전기아연도금강판의 제조방법에 관한 것으로, 보다 상세하게는 알루미늄 이온을 첨가한 염화물계 도금액에 의해 표면외관이 우수한 전기아연 도금강판을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an electro-zinc plated steel sheet having excellent surface appearance, and more particularly, to a method for producing an electro-zinc plated steel sheet having excellent surface appearance by using a chloride plating solution containing aluminum ions.
통상 냉연강판의 내식성을 향상시키기 위한 방법으로 아연도금이 개발 되었으며, 전기도금법과 용융도금법, 진공증착법등으로 제조되고 있다.In general, zinc plating has been developed as a method for improving the corrosion resistance of cold rolled steel sheets, and has been manufactured by electroplating, hot dip plating, and vacuum deposition.
이중 전기아연도금강판은 용융아연도금강판에 비해 도금부착량 조절이 용이하고 박도금이 가능하며, 아연 도금층의 표면외관이 양호하다.Compared to the hot-dip galvanized steel sheet, the electro-galvanized steel sheet is easier to control the coating amount and thin plating, and the surface appearance of the galvanized layer is good.
그러므로 종래에는 주로 도장처리용으로 사용되었으나, 최근에는 수요가의 요구에 따라 인산염처리 또는 크로메이트처리 및 유기수지를 도포처리하여 내직성, 내지문성 또는 윤활성등의 기능을 부여함으로써 가전, 자동차 등에 폭넓게 사용되고 있다.Therefore, in the past, it was mainly used for coating treatment, but recently, it is widely used in home appliances, automobiles, etc. by giving phosphate treatment, chromate treatment, and organic resin coating treatment according to the demand of the application to give functions such as weaving resistance, fingerprint resistance, or lubricity. have.
이와같은 전기아연도금강판에서 아연도금층의 표면물성이 불량한 경우, 상기와 같은 여러 가지 후처리 공정(인산염처리, 크로메이트처리, 내지문 또는 윤활수지피복처리)을 거친다 하더라도 전기도금층의 불량이 그대로 전사되어 표면불량이 선명해질 뿐만 아니라 일부는 분체 또는 전착도장처리 후에도 도장외관 및 선영성에 좋지 않은 영향을 미치게 된다.If the surface properties of the zinc plated layer is poor in such an electrogalvanized steel sheet, even after the various post-treatment processes (phosphate treatment, chromate treatment, anti-fingerprint or lubricant resin coating treatment), the defect of the electroplating layer is transferred as it is. Not only the surface defects become clear, but also some of them have a bad effect on the appearance and clarity of the coating even after powder or electrodeposition coating.
따라서 전기아연도금강판을 상기와 같은 용도로 사용하기 위해서는 아연도금층의 표면물성 즉, 표면외관의 균일성 및 백색도와 광택도가 우수해야 한다.Therefore, in order to use the electro-galvanized steel sheet as described above, 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 표면품질이 우수한 전기아연도금강판을 제조하기 위해서는 전기아연도금층의 표면물성에 큰 영향을 미치는 요인인 도금작업 조건을 최적으로 관리하면서 도금을 실시해야만 하며, 상기와 같은 문제점을 해결하기 위해서는 도금액 중에 유기 또는 무기물 첨가제를 첨가시키는 방법이 효과적인 것으로 알려지고 있다.In order to manufacture the electro-galvanized steel sheet having excellent surface quality as described above, the plating should be performed while optimally managing the plating operation conditions, which have a great influence on the surface properties of the electro-galvanized layer, and to solve the above problems. It is known that a method of adding an organic or inorganic additive to the plating liquid is effective.
염화물계 도금액의 경우 일본국 특허공개공보 소42-8764호에 게재된 폴리에틸렌 옥사이드 알킬레이트 술폰 화합물을 도금액에 첨가하는 방법과, 일본국 특허공개공보 제 소46-40402호에 게재된 카드뮴 이온을 도금액에 첨가하는 방법, 그리고 일본국 특허공개공보 제 소58-26438호에 게재된 NH4Cl, KCl, NaCl, AlCl3, BaCl2, CaCl2, FeCl2, FeCl3, MgCl2및 MnCl2중 적어도 1가지 이상을 100∼400g/l 함유하는 도금액에서 도금하는 방법등이 있다.In the case of the chloride-based plating solution, a method of adding the polyethylene oxide alkylate sulfone compound disclosed in Japanese Patent Application Laid-Open No. 42-8764 to the plating solution, and a cadmium ion disclosed in Japanese Patent Publication No. 46-40402 At least one of NH 4 Cl, KCl, NaCl, AlCl 3 , BaCl 2 , CaCl 2 , FeCl 2 , FeCl 3 , MgCl 2 and MnCl 2 as disclosed in Japanese Patent Application Laid-Open No. 58-26438. The plating method in the plating liquid containing 100-400 g / l or more of 1 or more types is mentioned.
그러나 상기의 폴리에틸렌 옥사이드 알킬레이트 술폰 화합물이나 카드뮴 이온을 도금액에 첨가하는 방법은 아연 도금층의 광택을 개선시키는 효과가 있으나, 도금액에서의 농도관리 및 분석이 어려우므로 품질편차를 발생할 우려가 있다.However, the method of adding the polyethylene oxide alkylate sulfone compound or cadmium ion to the plating liquid has an effect of improving the glossiness of the zinc plating layer, but there is a concern that quality deviation may occur because concentration control and analysis in the plating liquid are difficult.
또, 상기의 NH4Cl, KCl, NaCl, AlCl3, BaCl2, CaCl2, FeCl2, FeCl3, MgCl2및 MnCl2중 적어도 1가지 이상을 100∼400g/l함유하는 도금액에서 도금하는 방법에서는 도금액중의 전도 보조제로서 여러 가지 염화물을 사용할 수 있으나, 일부 금속염의 경우 도금층에 공석됨으로써 오히려 불순물로 작용하거나 과량의 무기금속 첨가에 의해 도금층 표면외관이 열화되는 문제점이 있었다.In addition, a method of plating at least one or more of the above 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 to 400 g / l Although various chlorides may be used as conduction aids in the plating solution, some metal salts have a problem of vacancy in the plating layer and thus acting as impurities or deteriorating the surface appearance of the plating layer by adding an excessive amount of inorganic metal.
따라서 본 발명의 목적은 상기와 같은 문제점들을 해결하기 위한 것으로서, 염화물을 이용한 전기아연도금강판 제조방법에 있어서, 도금액중에 알루미늄 이온을 첨가함으로써, 폭 넓은 전해조건에서 전기 아연도금층의 표면외관을 미려하고 균일하게 하며, 표면의 백색도와 광택도가 우수한 전기 아연도금강판의 제조방법을 제공하는 것이다.Therefore, an object of the present invention is to solve the above problems, in the method of manufacturing an electro-galvanized steel sheet using chloride, by adding aluminum ions in the plating solution, the surface appearance of the electro-galvanized layer in a wide range of electrolytic conditions It is to provide a method for producing an electro-galvanized steel sheet uniformity, excellent surface whiteness and gloss.
본 발명은 전기아연도금강판의 제조방법에 있어서, 아연이온 농도가 0.69∼2.29몰/ℓ, 염소이온농도가 2.26∼11.28몰/ℓ로서 아연이온에 대한 염소 이온 농도비([Cl-]/[Zn2+])가 3.32∼7.38이며, 알루미늄 이온농도가 0.005∼0.5몰/ℓ인 도금액의 pH를 2.0∼6.0의 범위로 조절하고, 도금액의 온도를 40∼70℃의 범위로 유지한 다음, 상대유속을 0.5∼3.0m/sec, 전류밀도를 20∼250A/dm2의 조건으로 하여 전기도금하는 것을 특징으로 하는 표면외관이 우수한 전기아연도금강판 제조방법에 관한 것이다.The present invention provides a zinc ion concentration of 0.69 to 2.29 mol / l and a chlorine ion concentration of 2.26 to 11.28 mol / l in the method for producing an electrogalvanized steel sheet (chlorine ion concentration ratio ([Cl − ] / [Zn)). 2+ ]) is 3.32 to 7.38, and the pH of the plating liquid having an aluminum ion concentration of 0.005 to 0.5 mol / l is adjusted to be in the range of 2.0 to 6.0, and the temperature of the plating liquid is maintained in the range of 40 to 70 ° C, and then the relative The present invention relates to a method for producing an electro-zinc plated steel sheet having excellent surface appearance, which is electroplated with a flow rate of 0.5 to 3.0 m / sec and a current density of 20 to 250 A / dm 2 .
이하, 본 발명을 상세하게 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에 따라 전기아연도금을 실시하는 경우, 도금액의 아연 이온농도가 0.69몰/ℓ 이하인 경우에는 아연 이온의 농도부족에 의해서 도금전압이 증가되며 도금층 조직이 커져 표면이 검게되는 탄도금(burning)을 일으키고, 2.29몰/ℓ 이상에서는 분말상태의 도금층이 나타나 도금밀착성이 떨어지기 때문에 아연 이온농도는 0.69∼2.29몰/ℓ로 유지하는 것이 바람직하다.In the case of conducting electro zinc plating according to the present invention, when the zinc ion concentration of the plating liquid is 0.69 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. It is preferable to maintain the zinc ion concentration at 0.69 to 2.29 mol / l because the plating layer in powder form appears at 2.29 mol / l or more, resulting in poor plating adhesion.
또한 염소 이온농도는 2.26몰/ℓ이하에서는 도금액이 전기전도도 감소로 인하여 탄도금이 발생할 우려가 있고, 11.28몰/ℓ이상에서는 도금액의 용해도 문제로 염소이온이 석출되어 도금작업성 및 도금액 농도관리에 문제점을 초래하고 이에따라 도금품질이 저하되므로, 염소 이온농도는 2.26∼11.26몰/ℓ로 조절하는 것이 바람직하다.In addition, chlorine ion concentration of 2.26 mol / ℓ or less, the plating solution may be a ballistic plating due to the reduction in electrical conductivity, and at 11.28 mol / ℓ or more chlorine ions are precipitated due to the solubility of the plating solution, the plating workability and plating solution concentration management Since it causes a problem and the plating quality deteriorates accordingly, it is preferable to adjust chlorine ion concentration to 2.26-11.26 mol / l.
또한 도금액 중 아연이온에 대한 염소이온의 상대 농도비 ([Cl-]/Zn2+])는 3.32∼7.38 범위로 유지되는데, 그 이유는 상기 상대 농도비가 3.32이하인 경우에는 도금액의 이온농도가 낮아 전기전도도가 감소되므로 도금전압이 증가될 뿐만아니라 아연도금층의 백색도 및 광택도가 감소되며, 7.38이상에서는 아연도금층의 백색도가 저하되고 도금줄무늬 발생이 증가되며, 또한 도금액 pH, 온도, 전류밀도 및 유속등의 도금조건 변화에 따른 표면외관 및 광택도의 변화가 크기 때문이다.그리고 도금액중의 알루미늄 이온농도 0.005몰/ℓ이하에서는 상기 상대 농도비가 4.61을 초과할 경우 알류미늄의 첨가효과가 미약하여, 고농도 염소 이온에 의해 아연 도금층의 백색도값이 저하될 뿐만 아니라, 도금줄무늬 발생이 심해질 우려가 있고, 0.5몰/ℓ이상에서는 알루미늄의 첨가에 의한 전기아연도금층의 표면외관 향상효과가 포화에 도달되므로, 도금액의 알루미늄 이온농도는 0.005∼0.5mol/1(Al 0.135∼13.5g/l)로 조절하는 것이 바람직하다.In addition, the relative concentration ratio of chlorine ions ([Cl − ] / Zn 2+ ]) to zinc ions in the plating liquid is maintained in the range of 3.32 to 7.38, because when the relative concentration ratio is 3.32 or less, the ion concentration of the plating liquid is low. As the conductivity is reduced, the plating voltage is not only increased, but also the whiteness and glossiness of the galvanized layer is decreased, and above 7.38, the whiteness of the galvanized layer is decreased and the occurrence of plating stripes is increased, and also the plating solution pH, temperature, current density and flow rate, etc. This is because the change in surface appearance and gloss is large due to the change of plating conditions. When the relative concentration ratio exceeds 4.61, the effect of adding aluminum is insignificant. Not only the whiteness value of the zinc plating layer is lowered by the ions, but also the plating streaks may be generated. Since the effect of improving the surface appearance of the electrogalvanized layer by the addition of saturation is reached, the aluminum ion concentration of the plating liquid is preferably adjusted to 0.005 to 0.5 mol / 1 (Al 0.135 to 13.5 g / l).
이와같은 알루미늄 이온은 Al 분말 또는 AlCl3, AlCl3, 6H2O등의 화합몰 형태로 첨가하는 것이 바람직하며, Al2(SO4)3, Al2(SO4)3.13∼14H2O, AlK(SO4)2.12H2O등의 황산염을 사용하는 것은 염화물계 도금액에 황산이온이 혼입되므로 바람직하지 않다.Such aluminum ions are preferably added in the form of Al powder or a compound mole such as AlCl 3 , AlCl 3 , 6H 2 O, and Al 2 (SO 4 ) 3 , Al 2 (SO 4 ) 3 .13-14H 2 O It is not preferable to use sulfates such as AlK (SO 4 ) 2 .12H 2 O because sulfate ions are mixed in the chloride plating solution.
상기 농도로 조성되는 도금액의 pH가 2.0이하에서는 아연도금층 표면이 어둡고 광택이 저하되며, 도금줄무늬 발생이 심하고, 6.0이상에서는 도금액중 아연이온이 수산화이온과 결합하여 수산화아연을 만들게 되어 도금액 농도 변화가 심하고 침전물이 생겨 도금표면이 거칠어지므로 도금액의 pH는 2.0∼6.0으로 제한하는 것이 바람직하다.When the pH of the plating liquid formed at the above concentration is 2.0 or less, the surface of the zinc plating layer is dark and gloss decreases, and plating streaks are severely generated. At 6.0 or above, zinc ions in the plating liquid are combined with hydroxide ions to form zinc hydroxide, thereby changing the plating solution concentration. It is preferable to limit the pH of the plating solution to 2.0 to 6.0 because it is severe and precipitates are formed and the plating surface becomes rough.
또한 도금액의 온도가 40℃이하에서는 아연 도금층의 백색도 및 광택이 저하되며, 70℃이상이 되면 도금줄무늬가 발생하고 도금액 증발이 심하여 농도편차가 발생될 뿐만 아니라 공해문제를 유발시키고, 도금작업성이 저하되므로 온도는 40∼70℃로 제한하는 것이 바람직하다.In addition, when the temperature of the plating liquid is lower than 40 ° C, the whiteness and gloss of the zinc plating layer are lowered. When the temperature of the plating liquid is higher than 70 ° C, plating streaks occur and plating liquid evaporates severely, resulting in concentration deviations, causing pollution problems, and plating workability. Since it lowers, it is preferable to limit temperature to 40-70 degreeC.
본 발명에서 상대유속은 강판에 대한 도금액의 상대 이동속도를 나타내며, 그 속도가 0.5m/sec미만일 경우에는 저속작업에 따른 도금중 표면 오염과 저전류밀도에 의해 도금표면이 거칠어지는 문제점이 있으며, 3.0m/sec이상인 경우에는 상대유속 증가에 따른 부대설비의 증가 및 도금액의 비산등의 문제점이 예상되므로 강판에 대한 도금액의 상대유속은 0.5∼3.0m/sec로 제한하는 것이 바람직하다.In the present invention, the relative flow rate represents the relative movement speed of the plating liquid relative to the steel sheet, and when the speed is less than 0.5 m / sec, there is a problem that the plating surface becomes rough due to surface contamination and low current density during plating due to the low speed operation. In case of more than 3.0m / sec, problems such as increase of auxiliary equipment and scattering of plating solution due to increase of relative flow rate are expected, so it is preferable to limit the relative flow rate of plating liquid to steel plate from 0.5 to 3.0m / sec.
한편, 상기와 같이 조절된 도금액을 사용하여 전기아연도금할 경우 전류 밀도는 20∼250A/dm2범위가 바람직한데, 그 이유는 전류밀도가 20A/dm2이하에서는 아연 도금층이 거칠어지고 표면외관이 불균일할 뿐만 아니라, 저전류밀도 조업으로 생산성이 떨어지며, 전류밀도가 250A/dm2이상에서는 한계전류밀도 범위를 넘계되어 도금표면이 검게되고 도금층 결정립이 크게 나타나는 탄도금이 발생되어 정상적인 아연도금의 품질을 얻을 수 없기 때문이다.On the other hand, when electro-galvanized using the plating liquid adjusted as described above, the current density is preferably in the range of 20 to 250 A / dm 2 , because the current density is 20 A / dm 2 or less, and the galvanized layer becomes rough and the surface appearance is In addition to non-uniformity, productivity decreases due to low current density operation, and when the current density exceeds 250A / dm 2 , the quality of normal zinc plating is generated due to the ballistic plating where the plating surface becomes black and the plating layer grains are large due to exceeding the limit current density range. Because you can't get it.
즉, 본 발명은 전기아연도금시 아연 이온농도와 염소 이온농도의 상대 농도비가 3.32∼7.38범위로 넓은 영역에서도 알루미늄 이온농도가 0.005∼0.5몰/ℓ로 유지되면, 도금액의 pH, 온도, 유속 및 전류밀도 등의 도금조건이 상기한 범위내에서 변화하는데에 관계없이 아연도금표면의 백색도 및 광택도가 높은 값을 유지할 뿐만 아니라 도금줄무늬 발생이 없고 외관의 균일성이 확보되어 연속라인에서 도금작업시 작업성이 용이해져 생산성을 증대시킬 수 있다.That is, in the present invention, when the aluminum ion concentration is maintained at 0.005 to 0.5 mol / l even in a region where the relative concentration ratio between zinc ion concentration and chlorine ion concentration is in the range of 3.32 to 7.38, the pH, temperature, flow rate and Regardless of the change of plating conditions such as current density within the above range, it maintains the high whiteness and glossiness of the galvanized surface, and does not generate plating streaks and ensures uniformity in appearance. Workability becomes easy and productivity can be increased.
이하, 본 발명을 실시예를 통해 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
본 발명의 알루미늄 이온의 첨가에 따른 효과를 알아보기 위해 두께 0.8㎜인 냉연강판을 전처리(알카리탈지, 산세)하고 염화물계 도금액인 하기 표 1에 나타난 도금액 농도 및 도금조건으로 전기아연도금강판을 제조하였으며, 전기아연도금층의 도금부착량은 20g/m2로 일정하게 하였다.In order to examine the effect of the addition of aluminum ions 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, which is a chloride-based plating solution. The plating amount of the electrogalvanized layer was constant at 20 g / m 2 .
상기와 같이 제조된 전기아연도금강판에 대한 도금표면의 백색도 및 광택도를 측정하였고, 도금줄무늬 발생정도를 관찰하고, 그 결과를 하기 표1에 나타내었다.The whiteness and glossiness of the plating surface of the electro-galvanized steel sheet prepared as described above were measured, and the degree of plating streaks was observed, and the results are shown in Table 1 below.
하기 표 1에 나타난 전기아연도금층의 표면의 백색도는 Color and Color Difference Meter C-5120(TOKYO DENSHOKU)에 의해 측정된 값(L*)이고, 광택도는 Gloss Meter (ERICH SEN)에 의하여 입사각 60°로 측정(G60)하였고, 도금외관의 도금줄무늬는 육안관찰찰에 의해 조사하였으며 각각의 평가는 하기와 같이 구분하여 나타내었다.The whiteness of the surface of the electro-galvanized layer shown in Table 1 is a value (L * ) measured by Color and Color Difference Meter C-5120 (TOKYO DENSHOKU), the glossiness is incident angle 60 ° by Gloss Meter (ERICH SEN) Measured by (G 60 ), the plating stripes of the plating appearance was examined by visual observation and each evaluation is shown as follows.
[표 1]TABLE 1
상기 표 1에 나타난 바와 같이, 본 발명의 제조방법대로 도금욕에 알루미늄이온을 0.005∼0.5몰/ℓ로 부가하여 도금한 도금재의 경우 도금액의 pH, 온도, 유속 및 전류밀도 등의 도금조건이 넓은 범위로 변화되어도 전기아연도금층의 백색도와 광택도가 높고, 도금줄무늬의 발생이 없이, 표면외관이 우수하여 균일성이 유지되지만 알루미늄이온이 첨가되지 않았거나 발명의 범위를 벗어나 과량 첨가된 도금용액으로 도금된 비교재(1∼2)에서는 도금층의 백색도 및 광택도가 낮고 도금중 표면외관이 좋지 않은 것을 알 수 있다.As shown in Table 1, in the case of the plated material coated with 0.005 to 0.5 mol / l of aluminum ions to the plating bath according to the manufacturing method of the present invention, the plating conditions such as pH, temperature, flow rate and current density of the plating solution are wide. Even if it is changed to a range, the electrolytic galvanized layer has high whiteness and gloss, and the surface appearance is excellent without the occurrence of plating streaks, so that the uniformity is maintained, but the plating solution is not added with aluminum ions or is in excess of the invention. In the plated comparative materials 1 to 2, it can be seen that the whiteness and glossiness of the plating layer are low and the surface appearance during plating is not good.
[실시예 2]Example 2
본 발명에 적합한 아연이온의 농도를 알아보기 위해 하기 표 2에 나타난 도금액 농도 및 도금조건으로 실시예 1과 동일한 방법으로 전기아연도금강판을 제조하였다.In order to determine the concentration of zinc ions suitable for the present invention, the electrolytic galvanized steel sheet was manufactured in the same manner as in Example 1 with the plating solution concentration and plating conditions shown in Table 2 below.
상기와 같이 제조된 전기아연도금강판에 대한 도금표면의 백색도 및 광택도, 및 도금줄무늬 발생정도를 실시예 1과 동일한 방법으로 관찰하고, 그 결과를 하기 표 2에 나타내었다.The whiteness and glossiness, and the degree of plating streaks of the plating surface of the galvanized steel sheet prepared as described above were observed in the same manner as in Example 1, and the results are shown in Table 2 below.
[표 2]TABLE 2
상기 표 2에 나타난 바와 같이, 본 발명에 적합한 아연이온의 농도범위(0./69∼2.29몰/ℓ)를 갖는 도금액으로 도금된 상기 실시예 1의 발명재 1-12와 비교할 때, 아연이온의 농도가 낮은 비교재 3의 경우 도금층의 표면이 검어 백색도가 나빴고 아연이온의 농도가 지나치게 많은 비교재 4의 경우도 도금층의 백색도 및 광택도가 낮고 도금줄무늬가 생기는 등 도금층의 표면외관이 좋지 못하였다.As shown in Table 2 above, when compared with the inventive material 1-12 of Example 1 plated with a plating liquid having a concentration range (0./69 to 2.29 mol / l) of zinc ions suitable for the present invention, zinc ions In the case of Comparative Material 3 having a low concentration of, the surface of the plating layer was bad due to the black surface and the Comparative Material 4 having too high concentration of zinc ions, the surface appearance of the plating layer was not good, such as the whiteness and gloss of the plating layer was low, and the plating streaks occurred. It was.
[실시예 3]Example 3
본 발명에 적합한 아연이온과 염소이온의 농도비 및 도금액의 유속을 알아보기 위해 하기 표 3에 나타난 도금액 농도 및 도금조건으로 실시예 1과 동일한 방법으로 전기아연도금강판을 제조하였다.In order to determine the concentration ratio of zinc ions and chlorine ions suitable for the present invention and the flow rate of the plating solution, an electrogalvanized steel sheet was prepared in the same manner as in Example 1 with the plating solution concentration and plating conditions shown in Table 3 below.
상기와 같이 제조된 전기아연도금강판에 대한 도금표면의 백색도 및 광택도, 및 도금줄무늬 발생정도를 실시예 1과 동일한 방법으로 관찰하고, 그 결과를 하기 표 3에 나타내었다.The whiteness and glossiness, and the degree of plating streaks of the plating surface of the electro-galvanized steel sheet prepared as described above were observed in the same manner as in Example 1, and the results are shown in Table 3 below.
[표 3]TABLE 3
상기 표 3에 나타난 바와 같이, 아연이온에 대한 염소이온의 상대농도비가 본 발명에 적합한 범위(3.32∼7.38)인 도금액으로 도금된 상기 실시예 1의 발명 재1-12와 비교할 때, 그 이하인 비교재 5의 경우 도금층의 광택도가 아주 낮고 도금줄무늬가 많이 생기는 등 도금층의 표면외관이 좋지 못하였고, 염소이온이 상대적으로 너무 많은 비교재 6의 경우 백색도가 아주 낮고 도금줄무늬가 많이 생기는 등 역시 도금층의 표면외관이 좋지 못하였다. 또한, 비교재 5와 같이 도금액의 유속이 너무 느린 경우에도 도금층의 광택도가 아주 낮고 도금줄무늬가 많이 생기는 등 도금층의 표면외관이 나빴다.As shown in Table 3, the relative concentration ratio of chlorine ions to zinc ions is less than that when compared with the inventive material 1-12 of Example 1 plated with a plating solution in the range (3.32 to 7.38) suitable for the present invention. In case of ash 5, the surface appearance of the plating layer was not good, such as the glossiness of the plating layer was very low and the plating stripe was formed a lot. The surface appearance of was not good. In addition, even when the flow rate of the plating liquid was too slow as in Comparative Material 5, the surface appearance of the plating layer was bad, such as the glossiness of the plating layer was very low and a lot of plating streaks occurred.
[실시예 4]Example 4
본 발명에 적합한 전류밀도를 알아보기 위해 하기 표 4에 나타난 도금액 농도 및 도금조건으로 실시예 1과 동일한 방법으로 전기아연도금강판을 제조하였다.In order to determine the current density suitable for the present invention, an electrogalvanized steel sheet was manufactured in the same manner as in Example 1 with the plating solution concentration and plating conditions shown in Table 4 below.
상기와 같이 제조된 전기아연도금강판에 대한 도금표면이 백색도 및 광택도, 및 도금줄무늬 발생정도를 실시예 1과 동일한 방법으로 관찰하고, 그 결과를 하기 표 4에 나타내었다.The plating surface of the galvanized steel sheet prepared as described above was observed in the same manner as in Example 1, the degree of whiteness and gloss, and the degree of plating streaks, and the results are shown in Table 4 below.
[표 4]TABLE 4
상기 표 4에 나타난 바와 같이, 전류밀도가 본 발명에 적합한 범위(20∼250A/dm2)범위인 조건에서 전기도금된 상기 실시예 1의 발명재1-12와 비교할 때, 그 이하인 비교재 7의 경우 아연 도금층이 거칠고 표면외관이 불균일하여 광택도가 나빴고, 그 이상에서 도금된 비교재 8의 경우는 도금표면이 검어 백색도가 떨어졌고 광택도도 좋지 못하였다.As shown in Table 4, the comparative material 7 is less than that when compared with the inventive material 1-12 of Example 1 electroplated under the condition that the current density is in the range suitable for the present invention (20 ~ 250A / dm 2 ) range The gloss was poor due to the roughness of the galvanized layer and the uneven appearance of the surface. In the case of Comparative Material 8 plated above, the plated surface was black, resulting in poor whiteness and poor gloss.
상기한 바와같이 본 발명은 염화물계 전기아연도금액에 있어서, 유기첨가제를 첨가시키지 않고 알루미늄 이온농도를 0.005∼0.5몰/리터 범위로 유지함으로써, 도금액중의 아연이온과 염소이온의 농도비가 넓은 범위로 변하하여도 도금강판의 표면외관이 변화하지 않으며, 다른 조건이 변화되어도 즉, 넓은 전해조건에서 아연 도금층의 표면외관이 균일하고, 백색도와 광택도가 양호하며, 도금줄무늬가 없는 표면외관이 우수한 전기아연도금강판을 제공할 수 있는 효과가 있다.As described above, the present invention provides a wide range of concentration ratios of zinc ions and chlorine ions in the plating solution by maintaining the aluminum ion concentration in the range of 0.005 to 0.5 mol / liter without adding an organic additive in the chloride type electro zinc plating solution. The surface appearance of the plated steel sheet does not change even if it is changed to. Even if other conditions are changed, the surface appearance of the zinc plated layer is uniform under a wide range of electrolytic conditions, the whiteness and gloss is good, and the surface appearance without plating is excellent. It is effective to provide an electro galvanized steel sheet.
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