KR100940669B1 - Zn-Ni Alloy Electrodeposition Electrolyte, Preparing Method of Zn-Ni Alloy Electrodeposited Steel Sheet and Steel Sheet Prepared Thereby Having Good Surface Appearance, Adhesion and Anti-Chipping - Google Patents
Zn-Ni Alloy Electrodeposition Electrolyte, Preparing Method of Zn-Ni Alloy Electrodeposited Steel Sheet and Steel Sheet Prepared Thereby Having Good Surface Appearance, Adhesion and Anti-Chipping Download PDFInfo
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Abstract
특정한 첨가제가 사용되는 도금층의 표면외관, 밀착성 및 저온 치핑성이 우수한 염화물계 아연-니켈 합금 전기 도금액, 이를 이용한 아연-니켈 합금 전기도금강판 제조방법 및 이에 따라 제조된 아연-니켈 합금 전기도금강판에 관한 것으로, 술폰산 나트륨 50-200g/L, 티오우레아 50-100g/L, 에틸알콜과 오르소 바닐린이 1:0.01~0.08 중량비로 혼합된 용액 10-60g/L 및 잔부 물로 이루어진 첨가제 0.5~8.0ml/L을 포함하며, 아연이온 농도 0.5-2.0몰, 니켈이온 농도 0.1-0.5몰, 그리고 염소 이온의 농도 6.0-9.0몰인 염소계 아연-니켈 합금 전기도금 조성물 및 이를 pH 2.5-4.5, 온도 50-70℃, 전류밀도 40-200A/dm2 및 도금액과 음극의 상대 유속 1.0-2.5m/sec으로 소지강판에 도금하는 아연-니켈 합금 전기도금강판 제조방법 및 이에 따라 제조된 아연-니켈 합금 전기도금 강판이 제공된다. 본 발명의 아연-니켈 합금전기도금 강판은 우수한 도금층 백색도 및 광택도와 같은 표면외관, 밀착성 및 저온 치핑성을 갖는다. Chloride-based zinc-nickel alloy electroplating solution having excellent surface appearance, adhesion and low temperature chipping property of a specific additive, a method of manufacturing zinc-nickel alloy electroplating steel sheet using the same, and a zinc-nickel alloy electroplating sheet manufactured accordingly. It is related with the additives which consists of sodium sulfonate 50-200g / L, thiourea 50-100g / L, 10-60g / L solution which ethyl alcohol and ortho vanillin are mixed by 1: 0.01 ~ 0.08 weight ratio, and the balance water 0.5-8.0 ml Chlorine-based zinc-nickel alloy electroplating composition comprising / L and having a zinc ion concentration of 0.5-2.0 mol, a nickel ion concentration of 0.1-0.5 mol, and a chlorine ion concentration of 6.0-9.0 mol, and a pH of 2.5-4.5, a temperature of 50-70 Manufacturing method of zinc-nickel alloy electroplating steel sheet plated on a steel sheet with a current density of 40-200A / dm 2 and a relative flow rate of 1.0-2.5m / sec of a plating solution and a cathode, and the zinc-nickel alloy electroplating sheet manufactured accordingly This is provided. The zinc-nickel alloy electroplated steel sheet of the present invention has surface appearance, adhesion and low temperature chipping properties such as excellent plating layer whiteness and glossiness.
아연-니켈 합금전기 도금액, 도금강판, 저온 치핑성Zinc-Nickel Alloy Electroplating Solution, Plated Steel Sheet, Low Temperature Chipping
Description
본 발명은 도금층의 표면외관, 밀착성 및 저온 치핑성이 우수한 염화물계 아연-니켈 합금 전기 도금액, 이를 이용한 아연-니켈 합금 전기도금강판 제조방법 및 이에 따라 제조된 아연-니켈 합금 전기도금강판에 관한 것이다. 보다 상세하게 본 발명은 특정하게 배합된 아연-니켈 합금 전기도금액용 첨가제가 사용되는 도금층의 표면외관, 밀착성 및 저온 치핑성이 우수한 염화물계 아연-니켈 합금 전기 도금액, 이를 이용한 아연-니켈 합금 전기도금강판 제조방법 및 이에 따라 제조된 아연-니켈 합금 전기도금강판에 관한 것이다.
The present invention relates to a chloride-based zinc-nickel alloy electroplating solution having excellent surface appearance, adhesion, and low temperature chipping properties of a plating layer, a method of manufacturing a zinc-nickel alloy electroplating steel sheet using the same, and a zinc-nickel alloy electroplating sheet prepared accordingly. . More specifically, the present invention provides a chloride-based zinc-nickel alloy electroplating solution having excellent surface appearance, adhesion, and low temperature chipping properties of a plating layer using a specially formulated additive for zinc-nickel alloy electroplating solution, and zinc-nickel alloy electroplating using the same. It relates to a plated steel sheet production method and a zinc-nickel alloy electroplated steel sheet produced accordingly.
아연 전기 도금재는 도금 내식성이 우수한 것으로 가전제품, 건설, 자동차용 소재 로 널리 사용되어 왔다. 그러나, 가혹한 분위기 하에서 내식성을 확보하기 위하여 아연도금층의 두께를 증가시켜야 하며 이로 인하여 비용의 증가 및 밀착성, 가공성 등이 저하된다.
Zinc electroplating material has excellent plating corrosion resistance and has been widely used for home appliances, construction and automobiles. However, in order to secure corrosion resistance under severe atmosphere, the thickness of the galvanized layer should be increased, resulting in an increase in cost, adhesion, and workability.
따라서 이러한 문제를 해결하기 위하여 아연-니켈 합금 전기도금이 개발되어 왔다. 이러한 아연-니켈 합금전기도금은 욕의 성분에 따라, 여러가지가 사용될 수 있으며, 그 중 황화물욕 및 산성욕을 포함하는 산성욕을 기본으로한 도금재의 생산 방식이 일반적으로 사용된다. Therefore, zinc-nickel alloy electroplating has been developed to solve this problem. The zinc-nickel alloy electroplating may be used in various ways depending on the components of the bath, and a production method of a plating material based on an acid bath including a sulfide bath and an acid bath is generally used.
염화물욕은 황화물욕에 비하여 전기 전도도가 우수하여 고 전류 밀도 도금에 적합한 것으로 알려져 있으며, 용해성 양극을 사용함으로 불용성 양극을 사용하는 황화물욕에 비하여 용액의 제어가 편리하고 비용이 저렴한 장점이 있다. 그러나, 염화물 도금욕에서 아연과 니켈의 큰 전위차로 인하여 아연 양극에 니켈의 무전해 치환에 의한 아연 수산화물계통의 슬러지가 발생되고 생성된 슬러지는 양극의 표면에 붙어서 연속작업에 의한 아연 용해시 불균일하게 용해되어 도금액의 농도를 현저하게 변화시키고, 통전을 방해하며, 도금 전압이 상승하고, 불균일한 전착성으로 도금층의 표면외관이 불량하게 된다. 또한, 슬러지 형태로 박리되어 용액에 슬러지가 혼입되면서 도금층의 밀착성이 떨어진다. 아연과 니켈의 전위차는 도금층이 형성될 때 온도가 저하된 곳에서 도금층의 내부 스트레스(internal stress)로 인해 박리가 쉽게 일어나게 하며 불량한 저온 치핑성을 나타낸다.
Chloride baths are known to be suitable for high current density plating due to their superior electrical conductivity compared to sulfide baths, and have the advantage of convenient solution control and low cost compared to sulfide baths using insoluble anodes by using soluble anodes. However, due to the large potential difference between zinc and nickel in the chloride plating bath, sludge of zinc hydroxide system is generated by electroless substitution of nickel on the zinc anode, and the produced sludge adheres to the surface of the anode, resulting in uneven dissolution of zinc by continuous operation. Melting significantly changes the concentration of the plating liquid, impedes the conduction, increases the plating voltage, and results in poor surface appearance of the plating layer due to uneven electrodeposition. In addition, as the sludge is peeled off in the form of sludge, the adhesion of the plating layer is inferior as the sludge is mixed in the solution. The potential difference between zinc and nickel causes the peeling to occur easily due to the internal stress of the plating layer where the temperature decreases when the plating layer is formed, and exhibits poor low temperature chipping.
이러한 문제를 해결하기 위한 종래 기술로서 일본 특허출원 소 59-211589는 염화아연 및 염화니켈을 주성분으로 하는 염화물욕 및 유산염을 혼합한 도금액에 염화 암모늄을 일부 첨가하고 도금조건을 변경하여 석출물에 부수적으로 수반되는 황갈색이나 청자색의 산화물의 혼입 석출을 유효하게 억제하는 바에 대하여 개시하고 있다. 그러나, 초기 약 100시간 정도까지는 산화물의 석출이 억제되나, 그 이상 조업시 다시 석출물이 나타나는 결점이 있다.
As a conventional technique for solving such a problem, Japanese Patent Application No. 59-211589 discloses adding ammonium chloride to the plating solution containing zinc chloride and nickel chloride as a main component, and adding a portion of ammonium chloride to the plating solution and changing the plating conditions, thereby adhering to the precipitate. Disclosed is a bar that effectively suppresses the mixing and precipitation of accompanying yellowish brown and blue violet oxides. However, the precipitation of oxide is suppressed up to about 100 hours at the beginning, but there is a drawback that precipitates appear again during further operation.
또한, 일반적인 방법으로 알코올을 첨가하여 양극의 용해성을 개선하는 방법이 알려져 있으나, 장시간 사용시 알코올의 휘발성에 의한 소모가 심하며 도금층의 밀착성도 개선되지 못한다. In addition, a method of improving the solubility of the positive electrode by adding alcohol as a general method is known, but when consumed for a long time is consumed by the volatility of alcohol is severe and the adhesion of the plating layer is not improved.
일본 특허 출원 번호 93-167094에는 유기화합물을 첨가함으로써 도금층에 탄소를 0.001-10wt% 함유시켜 가공성을 개선하는 바에 대하여 개시하고 있으나, 밀착성이 열악해지는 결점이 있다. 또한 일본 특허 공보 제 2761470에서는 분자량이 400-800인 폴리에틸렌 글리콜과 니코틴산, 우레아, 티오우레아, 니코틴아미드, 티오글리콜산과 같은 비이온성 계면활성제 중 하나 이상의 화합물을 첨가하여 침상결함을 향상시키고 탄도금 면적을 감소시키는 바에 대하여 개시하고 있으나, 표면 광택도 및 밀착성이 저하되는 결과를 나타낸다.
Japanese Patent Application No. 93-167094 discloses the addition of an organic compound to improve the workability by containing 0.001-10 wt% of carbon in the plating layer, but has a drawback of poor adhesion. In addition, Japanese Patent Publication No. 2761470 adds one or more compounds of polyethylene glycol having a molecular weight of 400-800 and nonionic surfactants such as nicotinic acid, urea, thiourea, nicotinamide, and thioglycolic acid to improve needle defects and improve ballistic area. Although it discloses about reducing, it shows the result that surface glossiness and adhesiveness fall.
또한, 본 발명자들은 대한민국 특허 출원공개 1999-0049604에서 안식향산과 계면활성제인 피-톨루엔술폰산으로 형성된 첨가제를 첨가하여 표면외관개선 및 밀착성을 개선하는 바에 대하여 개시하고 있으며, 대한민국 특허공개 2001-0061574에는 술폰산 나트륨과 오바닐린을 첨가하여 도금층의 조도, 밀착성, 가공성등을 개선한 바 있다. 대한민국 특허 출원번호 2002-0051276에는 티오우레아 및 술폰산나트륨등을 첨가하여 조도, 백색도 및 탄도금을 개선하는 바에 대하여 개시하고 있다. 상기 특허출원들은 도금층의 표면외관 및 밀착성 등은 개선하고 있으나, 저온에서(영하 20도 이하) 치핑성은 개선시키지 못하였다.
In addition, the present inventors disclose that in the Republic of Korea Patent Application Publication No. 1999-0049604 to improve the surface appearance improvement and adhesion by adding an additive formed from benzoic acid and a surfactant P-toluenesulfonic acid, and the Republic of Korea Patent Publication 2001-0061574 The addition of sodium and vanillin have improved the roughness, adhesion, and workability of the plating layer. Korean Patent Application No. 2002-0051276 discloses the addition of thiourea and sodium sulfonate to improve roughness, whiteness, and ballistic plating. The patent applications improve the surface appearance and adhesion of the plating layer, but do not improve the chipping property at low temperatures (below minus 20 degrees).
일본특허 공개 제 2002-129376에서는 도금층의 아연과 니켈 함량비를 조절하여 저온 치핑을 개선하고 있으나, 도금시 전류 투입비나 도금액등을 이중 관리하여야 함으로 용이성이 떨어지며 비용이 증가되는 단점이 있다.
Japanese Patent Laid-Open Publication No. 2002-129376 improves low temperature chipping by adjusting the zinc and nickel content ratio of the plating layer, but has a disadvantage in that the ease of use is reduced and the cost is increased due to the dual management of the current input ratio or the plating solution.
이에 본 발명의 목적은 도금시 도금층의 표면외관, 밀착성 및 저온 치핑성을 증진시키는 아연-니켈 합금 전기도금 조성물을 제공하는 것이다.
Accordingly, it is an object of the present invention to provide a zinc-nickel alloy electroplating composition which promotes the surface appearance, adhesion and low temperature chipping of the plating layer during plating.
본 발명의 다른 목적은 도금층의 표면외관, 밀착성 및 저온 치핑성을 증진시키는 아연-니켈 합금 전기도금강판 제조방법을 제공하는 것이다.
Another object of the present invention is to provide a method for producing a zinc-nickel alloy electroplated steel sheet to enhance the surface appearance, adhesion and low temperature chipping of the plating layer.
본 발명의 또 다른 목적은 도금층의 표면외관, 밀착성 및 저온 치핑성을 증진된 아연-니켈 합금 전기도금강판을 제공하는 것이다.
It is still another object of the present invention to provide a zinc-nickel alloy electroplated steel sheet having improved surface appearance, adhesion and low temperature chipping of the plating layer.
본 발명의 일 견지에 의하면, According to one aspect of the invention,
술폰산 나트륨 50-200g/L, 티오우레아 50-100g/L, 에틸알콜과 오르소 바닐린이 1:0.01~0.08 중량비로 혼합된 용액 10-60g/L 및 잔부 물로 이루어진 첨가제 0.5~8.0ml/L을 포함하며, 아연이온 농도 0.5-2.0몰, 니켈이온 농도 0.1-0.5몰, 그리고 염소 이온의 농도 6.0-9.0몰인 염소계 아연-니켈 합금 전기도금 조성물이 제공된다.
50-200 g / L sodium sulfonate, 50-100 g / L thiourea, 0.5-8.0 ml / L of additives consisting of 10-60 g / L of a solution in which ethyl alcohol and ortho vanillin are mixed at a weight ratio of 1: 0.01 to 0.08 And a chlorine-based zinc-nickel alloy electroplating composition having a zinc ion concentration of 0.5-2.0 mol, a nickel ion concentration of 0.1-0.5 mol, and a chlorine ion concentration of 6.0-9.0 mol.
본 발명의 다른 견지에 의하면, According to another aspect of the present invention,
상기 본 발명의 염소계 아연-니켈 합금 전기도금 조성물을 pH 2.5 - 4.5, 온도 50 - 70℃, 전류밀도 40-200A/dm2 및 도금액과 음극의 상대 유속 1.0 - 2.5m/sec으로 소지강판에 도금하는 아연-니켈 합금 전기도금강판 제조방법이 제공된다. The chlorine-based zinc-nickel alloy electroplating composition of the present invention is plated on a steel sheet at a pH of 2.5-4.5, a temperature of 50-70 ° C, a current density of 40-200A / dm 2 and a relative flow rate of 1.0-2.5m / sec of the plating solution and the cathode. A zinc-nickel alloy electroplated steel sheet manufacturing method is provided.
본 발명의 또 다른 견지에 의하면, According to another aspect of the present invention,
상기 본 발명의 방법으로 도금된 아연-니켈 합금 전기도금 강판이 제공된다.
A zinc-nickel alloy electroplated steel sheet plated by the method of the present invention is provided.
이하, 본 발명에 대하여 상세히 설명한다.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명의 염소계 아연-니켈 합금 전기도금 조성물(이하, '전기도금 조성물' 이라 한다.)은 염화아연 및 염화니켈을 포함하며 나아가, 염화이온 농도는 또한, 염화칼륨 및 염화암모늄등으로 조절되는 것을 기본으로 하는 염화물욕 전기도금 조성물에 특정한 첨가제를 첨가하여 도금함으로써 도금층의 표면외관, 밀착성 및 저온 치핑성이 향상된다.
The chlorine-based zinc-nickel alloy electroplating composition of the present invention (hereinafter referred to as 'electroplating composition') includes zinc chloride and nickel chloride, and furthermore, the chloride ion concentration is also based on being controlled by potassium chloride, ammonium chloride, or the like. By adding a specific additive to the chloride bath electroplating composition, the surface appearance, adhesion and low temperature chipping of the plating layer are improved.
상기 염화아연, 염화니켈, 염화칼륨 및 염화암모늄등을 포함하는 기본 염화물욕에서 염화아연의 아연이온 몰농도는 0.5~2.0몰, 염화니켈의 니켈이온 몰농도는 0.1~5.0몰 그리고 염화물욕중 총 염화물에 의한 염소이온의 몰농도는 6.0~9.0몰로 구성된다.
In the basic chloride bath containing zinc chloride, nickel chloride, potassium chloride and ammonium chloride, the zinc ion molar concentration of zinc chloride is 0.5 to 2.0 moles, the nickel ion molar concentration of nickel chloride is 0.1 to 5.0 moles, and the total chloride in the chloride bath. The molar concentration of chlorine ion by is composed of 6.0 ~ 9.0 mol.
상기 도금액중 아연이온 농도가 0.5몰 미만인 경우에는 도금에 총금속 이온의 부족으로 검게 그을리는 자국(burning)이 발생하며, 2.0몰을 초과하는 경우에는, 분말 형태로 도금되어 밀착성이 떨어진다. 니켈의 농도가 0.1몰 미만인 경우에는, 도금층의 합금에서 니켈 함량이 10%이상 확보되지 않아 내식성이 감소되며, 0.5몰을 초과하는 경우에는 도금층의 니켈 함량이 16% 이상이 되어서 가공성 및 저온 치핑성이 감소된다. 염소 이온이 6.0몰 미만인 경우, 전기 전도도의 감소로 인하여 표면탄 도금이 다량 발생하고, 9.0몰을 초과하는 경우에는 용해도가 감소되어 염화 이온이 석출된다.
When the zinc ion concentration in the plating liquid is less than 0.5 mol, burning blacking occurs due to lack of total metal ions in the plating, and when it exceeds 2.0 mol, plating is performed in a powder form, resulting in poor adhesion. If the concentration of nickel is less than 0.1 mol, corrosion resistance is reduced since the nickel content is not more than 10% secured in the alloy of the plating layer, and if it exceeds 0.5 mol, the nickel content of the plating layer is 16% or more, so that workability and low temperature chipping resistance are increased. Is reduced. When the chlorine ion is less than 6.0 mol, a large amount of surface charcoal plating occurs due to the decrease in the electrical conductivity, and when it exceeds 9.0 mol, the solubility is reduced to precipitate chloride ions.
상기 염화물욕 도금액에 술폰산나트륨 50-200g/L, 티오우레아 50-100g/L, 에틸알콜과 오르소바닐린이 1:0.01~0.08 중량비로 혼합된 용액 10-60g/L 및 잔부 물로된 첨가제가 0.5~8.0ml/L로 첨가된다.
50-200 g / L of sodium sulfonate, 50-100 g / L of thiourea, 10-60 g / L of a solution in which ethyl alcohol and ortho vanillin are mixed in a weight ratio of 1: 0.01 to 0.08 in the chloride bath plating solution, and an additive of 0.5% Is added at -8.0 ml / L.
상기 첨가제중의 술폰산나트륨의 농도가 50g/L 미만이면, 전류밀도가 100A/dm2이상에서 입자의 미세화가 일어나지 않고 국부적인 입자 조대화를 보이며 도금층 표면에 줄상의 흙갈색 무늬가 발생한다. 이는 전류의 균일화 효과가 떨어지기 때문에 기인되는 것으로 여겨진다. 술폰산나트륨의 농도가 200g/L를 초과하는 경우에는 농도의 과다로 의한 전도성 감소로 도금층의 밀착성이 떨어지게 된다.
If the concentration of sodium sulfonate in the additive is less than 50 g / L, micronization of particles does not occur at a current density of 100 A / dm 2 or more, and local grain coarsening occurs. This is believed to be due to the inferior effect of the equalization of the current. When the concentration of sodium sulfonate exceeds 200 g / L, the adhesion of the plating layer is reduced due to the decrease in conductivity due to the excessive concentration.
티오우레아의 농도가 50g/L 미만이면, 표면탄도금 억제가 전류밀도 100A/dm2 이하에서 이루어지지 않으며, 100g/L을 초과하는 경우에는 우레아와 금속이온의 상호작용에 따른 표면 회색이 나타나며, 이온간 전위차의 개선이 이루어지지 않아 저온 치핑성을 개선시키지 못한다.
If the concentration of thiourea is less than 50 g / L, surface ballistic suppression is not performed at a current density of 100 A / dm2 or less. If the concentration of the thiourea is higher than 100 g / L, a surface gray is generated due to the interaction between urea and metal ions. The improvement of the interpotential difference is not achieved and thus the low temperature chipping property is not improved.
에틸알콜과 오르소 바닐린는 1:0.01~0.08중량비로 혼합되어 사용된다. 중량비가 1:0.01미만이면 첨가제의 첨가에 의한 밀착성과 저온 치핑성의 효과를 나타내지 못하며 1:0.08을 초과하는 경우에는 오르소 바닐린이 상온에서 과포화된 입자로 존재하여 용해되기 어렵다.
Ethyl alcohol and ortho vanillin are mixed in a ratio of 1: 0.01 to 0.08 weight. If the weight ratio is less than 1: 0.01, it does not show the effect of adhesion and low temperature chipping by the addition of additives, and if it exceeds 1: 0.08, ortho vanillin is present as supersaturated particles at room temperature and is difficult to dissolve.
첨가제중 상기 에틸알콜과 오르소 바닐린 혼합물의 함량은 10g/L~60g/L이다. 10g/L미만인 경우, 금속 이온간 전위차를 개선시키지 못하여 내부응력을 낮추지 못하여 저온 치핑성 향상 효과가 나타나지 않으며, 60g/L를 초과하는 경우에는 알코올이 쉽게 증발되며, 또한 강판 표면에 첨가제가 다량 흡착되어 이온의 강판 밀착을 방해한다.
The content of the ethyl alcohol and ortho vanillin mixture in the additive is 10g / L ~ 60g / L. If it is less than 10g / L, it does not improve the potential difference between metal ions and it does not lower the internal stress, so it does not show the effect of low temperature chipping property.If it exceeds 60g / L, alcohol is easily evaporated and additives are adsorbed on the surface of steel sheet. This prevents the adhesion of ions to the steel sheet.
상기와 같이 조성되는 첨가제는 염화물계 도금욕에 0.5ml/L~8.0ml/L로 첨가된다. 첨가량이 0.5ml/L 미만이면 그 첨가량이 적어 목적하는 품질개선 효과가 달성되지 않으며, 8.0ml/L 을 초과하는 경우에는 오히려 다량의 첨가제가 금속이온의 이동을 방해하여 도금액의 전도도가 감소되며, 따라서, 도금층 밀착성 및 저온 치핑성이 감소된다.
The additive composition as described above is added to the chloride-based plating bath in 0.5ml / L ~ 8.0ml / L. If the added amount is less than 0.5ml / L, the added amount is small so that the desired quality improvement effect is not achieved.If the added amount is more than 8.0ml / L, rather than a large amount of additives interfere with the movement of metal ions, the conductivity of the plating solution is reduced, Therefore, plating layer adhesion and low temperature chipping property are reduced.
상기 도금조성물의 온도는 50-70℃인 것이 바람직하다. 50℃ 미만의 온도에서는 도금층의 색상이 어두워지며 밀착성이 떨어진다. 70℃를 초과하면 도금 줄무늬 현상이 심하게 되며 도금층의 조도가 열악해진다. 도금용액의 pH는 2.5~4.5가 바람직하다. pH 2.5 미만에서는 도금표면이 어둡고 반광택 상태가 되며, pH 4.5를 초과하는 경우에는 용액에 용해된 불순 이온의 슬러지화에 의해 도금액이 오염된다. It is preferable that the temperature of the said plating composition is 50-70 degreeC. At a temperature below 50 ° C., the color of the plating layer becomes dark and adhesion is poor. If the temperature exceeds 70 ° C, the plating stripe phenomenon becomes severe and the roughness of the plating layer is poor. The pH of the plating solution is preferably 2.5 to 4.5. If the pH is less than 2.5, the plating surface becomes dark and semi-gloss. If the pH is higher than 4.5, the plating liquid is contaminated by sludge of impurity ions dissolved in the solution.
나아가, 도금조성물의 전류밀도는 40-200A/dm2가 바람직하다. 40A/dm2미만에서는 도 금층의 광택이 저하되며, 200A/dm2를 초과하는 경우에는 전류가 강판 에지에 집중되어 탄도금 현상이 나타난다.
Furthermore, the current density of the plating composition is preferably 40-200 A / dm 2 . If it is less than 40A / dm 2 , the gloss of the plating layer is lowered. If it is more than 200A / dm 2 , the current is concentrated at the edge of the steel sheet and a ballistic phenomenon occurs.
도금유속에 있어서, 도금조성물과 음극의 상대유속은 1.0~2.5 m/sec가 바람직하다. 강판과의 상대유속이 1.0m/sec 미만인 경우에는 적정 전류밀도가 협소하게 되고 전류밀도가 높은 영역에서는 도금 결정립이 조대해지며 이온의 전달이 느려져 탄도금이 발생하며, 2.5m/sec를 초과하는 상대유속은 연속 전기 도금 설비상 확보가 어려운 유속에 해당된다.
In the plating flow rate, the relative flow rate of the plating composition and the cathode is preferably 1.0 to 2.5 m / sec. When the relative flow rate with the steel sheet is less than 1.0 m / sec, the proper current density becomes narrow, and in the region where the current density is high, the plating grain is coarse and the transfer of ions is slow, which causes ballistic plating and exceeds 2.5 m / sec. Relative flow rates correspond to flow rates that are difficult to secure on a continuous electroplating installation.
본 발명에 의한 첨가제를 포함하는 도금조성물 및 도금방법으로 도금된 아연-니켈 합금 전기도금 강판은 도금층의 입자가 미세화되고 조직의 면형성 방위를 변화되어 백색도 및 광택도와 같은 표면외관이 향상된다. 또한, 이러한 입자 미세화에 의하여 가공시 도금층의 밀착성이 향상되며, 도금층 형성시 아연과 니켈의 전위차이가 감소되어 도금층의 내부 스트레스가 감소되며, 따라서, 저온 치핑성이 개선된다.
In the plating composition including the additive according to the present invention and the zinc-nickel alloy electroplating steel plate plated by the plating method, the particles of the plating layer are fined and the surface formation orientation of the tissue is changed to improve surface appearance such as whiteness and glossiness. In addition, the adhesion of the plated layer during processing is improved by the micronization of the particles, and the potential difference between zinc and nickel is reduced during the formation of the plated layer, thereby reducing the internal stress of the plated layer, thus improving the low temperature chipping.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.
Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예] EXAMPLE
소지금속으로 냉연강판에 아연이온 1.1몰/리터, 니켈이온 0.18몰/리터 및 염소이온 7몰/리터에 하기 표 1과 같이 구성되는 첨가제가 각각 표 1에 기재된 양으로 첨가된 도금액을 온도 62℃, pH 4, 도액과 음극의 상대유속 1.5m/sec, 전류밀도 100A/dm2 도금조건으로하여 도금량을 35g/m2으로 적용하여 비교예 및 발명예의 시편을 제조하였다. 도금층의 니켈을 13~13.2%로 조절하여 각 시편의 물성을 평가하여 하기 표 1에 나타내었다. The plating solution in which the additives composed of zinc ion 1.1 mol / liter, nickel ion 0.18 mol / liter and chlorine ion 7 mol / liter in the cold rolled steel sheet as the base metal in the amounts shown in Table 1, respectively, was added at a temperature of 62 ° C. The specimens of Comparative Examples and Inventive Examples were prepared by applying a plating amount of 35 g / m 2 at a pH of 4, a relative flow rate of 1.5 m / sec and a current density of 100 A / dm 2 of plating solution and cathode. The nickel of the plating layer was adjusted to 13 to 13.2% to evaluate the physical properties of each specimen and are shown in Table 1 below.
도금층의 백색도는 색차계(Color Difference Meter)로 측정하여, 70이상을 양호, 70이만을 불량으로 평가하였다. The whiteness of the plating layer was measured by a color difference meter, and 70 or more was evaluated as good and 70 was as poor.
광택도는 Erichsen의 광도기(Glossy Meter)로 측정하여 광택이 75이상인 경우를 양호, 그 미만을 불량으로 평가하였다. Glossiness was measured by Erichsen's Gloss Meter to evaluate the gloss of 75 or more and to evaluate the defect as poor.
도금층의 밀착성은 시편을 120o 구부려서 압축되는 부위에 테이프를 밀착시켜 도금층이 묻어나지 않은 경우를 양호, 묻어나는 경우를 불량으로 평가하였다. The adhesion of the plated layer was evaluated to be good and the case where the plated layer was not buried by adhering the tape to a portion compressed by bending the specimen 120 ° .
도금의 저온 치핑성은 강판에 아연-니켈 합금 전기도금을 행한 후, 일반적인 자동차사 조건으로 인산염 처리하고, 자동차사에서 사용되는 에폭시아민 도료를 이용하여 25um 두께로 1차 전착도장(조건:양이온 도장, 28℃, 300V에서 180초 유지, 170℃에서 15분간 소부(자동차사조건)) 및 30um 두께로 폴리에스테르계 수지의 스프레이 도장(조건: 스프레이 압력 3.0kgf/㎠, 145℃에서 20분간 소부(자동차사조건))한 후, 온도 -20℃에서 3시간 유지시킨 후 공압 2kgf/cm2으로 쇄석 (직경 0.5cm)을 쏘아서 표면에서 박리되는 도금층의 박리면적을 조사하여 4mm이하가 쏜 쇄석수의 10%미만은 양호, 그 이상은 불량으로 평가하였다. (일본 마쯔다 자동차사 조건)Low-temperature chipping is performed by electroplating zinc-nickel alloy on the steel plate, followed by phosphate treatment under general automotive conditions, and primary electrodeposition coating with a thickness of 25 um using an epoxy amine paint used in automobile companies (conditions: cationic coating, 180 seconds at 28 ℃, 300V, baked for 15 minutes at 170 ℃ (automotive condition) and spray coating of polyester resin at 30um thickness (condition: spray pressure 3.0kgf / ㎠, 20 minutes at 145 ℃) 4) After holding for 3 hours at -20 ℃, shoot crushed stone (diameter 0.5cm) with pneumatic pressure of 2kgf / cm 2 , and examine the peeling area of the plating layer peeled off from the surface. Less than% was evaluated as good and more than that. (Matsuda Motor Company conditions in Japan)
* 상기 첨가제 조성에서 잔부는 물임. * The balance in the additive composition is water.
본 발명의 방법으로 도금된 아연-니켈 합금전기도금 강판은 우수한 도금층 백색도 및 광택도와 같은 표면외관, 밀착성 및 저온 치핑성을 나타낸다. Zinc-nickel alloy electroplated steel sheets plated by the method of the present invention exhibit excellent surface appearance, adhesion and low temperature chipping, such as excellent plating layer whiteness and glossiness.
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