KR100370569B1 - ADDITIVE ADDED Zn-Fe ALLOY ELECTROPLATING SOLUTION AND METHOD FOR MANUFACTURING COATED STRIP USING THE SAME - Google Patents

ADDITIVE ADDED Zn-Fe ALLOY ELECTROPLATING SOLUTION AND METHOD FOR MANUFACTURING COATED STRIP USING THE SAME Download PDF

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KR100370569B1
KR100370569B1 KR1019960019279A KR19960019279A KR100370569B1 KR 100370569 B1 KR100370569 B1 KR 100370569B1 KR 1019960019279 A KR1019960019279 A KR 1019960019279A KR 19960019279 A KR19960019279 A KR 19960019279A KR 100370569 B1 KR100370569 B1 KR 100370569B1
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iron
alloy electroplating
electroplating solution
additive
zinc
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KR1019960019279A
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KR970074983A (en
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김현태
진영술
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주식회사 포스코
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/565Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/02Heating or cooling
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/12Process control or regulation

Abstract

PURPOSE: An additive added Zn-Fe alloy electroplating solution is provided to improve precipitation of iron and obtain coating layer having superior surface roughness and surface external appearance by adding an additive comprising polyethylene glycol, aromatic acid and propargyl alcohol (C3H4O) to zinc chloride-iron alloy plating pot, and a method for manufacturing coated strip using the same is provided. CONSTITUTION: In a Zn-Fe alloy electroplating solution comprising 0.8 to 2.0 mole/L of mole concentration of zinc ions in zinc chloride, 0.15 to 0.5 mole/L of mole concentration of iron ions in iron chloride and 5.0 to 9.0 mole/L of mole concentration of chlorine ions, wherein a mole ratio of iron ions (zinc ions+iron ions) is 0.08 to 0.3 : 1, the additive added Zn-Fe alloy electroplating solution is characterized in that an additive is added to the Zn-Fe alloy electroplating solution in a concentration of 0.5 to 6.0 ml/L, wherein the additive is prepared by adding aromatic acid and propargyl alcohol to an aqueous solution in which concentration of the mixed polyethylene glycol is 10 to 15% in such a way that 0.1 to 5.0 wt.% of aromatic acid and 0.01 to 1.0 wt.% of propargyl alcohol are contained in the mixed polyethylene glycol after preparing mixed polyethylene glycol in which a mixing ratio of the polyethylene glycols is 1:2-1:5 by weight ratio by mixing one or more of polyethylene glycols {£H(COH2CH2)n|OH} whose polymerization degree (n) is in the range of 10 to 20 and 20 to 30, respectively. The method for manufacturing coated strip using the additive added Zn-Fe alloy electroplating solution is characterized in that electroplating is performed in the state that a relative flow rate of the Zn-Fe alloy electroplating solution and cathode is 0.5 to 2.5 m/sec using the additive added Zn-Fe alloy electroplating solution having pH of 1.0 to 5.0, temperature of 40 to 70 deg.C and current density of 20 to 200 A/cm¬2.

Description

첨가제가 첨가된 아연-철 합금전기도금용의 용액 및 이를 이용한 도금 강판 제조방법Solution for Zinc-Iron Alloy Electroplating with Additive and Method for Manufacturing Plated Steel Sheet Using the Same

본 발명은 첨가제가 첨가된 아연-철 합금전기도금용의 용액 및 이를 이용한 도금강판 제조방법에 관한 것으로, 특히 염화아연과 염화철에 염화칼륨, 염화칼슘, 염화나트륨, 염화암모늄 등의 지지전해질 1종 혹은 2종 이상의 혼합물로 구성되는 염화물계 아연-철 합금 도금욕에 폴리에틸렌글리콜과 방향족산 및 프로파질알콜(Propagyl Alcohol : C3H4O)로 구성되는 첨가제를 첨가하여 철석출이 향상되고, 표면조도가 우수하며, 표면외관(백색도, 광택도)이 양호한 도금층을 얻을 수 있는 첨가제가 첨가된 아연-철 합금전기도금용 용액 및 이를 이용한 도금강판 제조방법에 관한 것이다.The present invention relates to a solution for electroplating a zinc-iron alloy to which an additive is added, and a method for producing a coated steel sheet using the same. More particularly, the present invention relates to a method for producing zinc chloride and iron chloride by adding one or two supporting electrolytes such as potassium chloride, calcium chloride, sodium chloride, The addition of an additive composed of polyethylene glycol and an aromatic acid and propagyl alcohol (C 3 H 4 O) to the chloride-based zinc-iron alloy plating bath composed of the above mixture improves iron precipitation and provides excellent surface roughness Iron alloy electroplating solution to which an additive capable of obtaining a plating layer having a good surface appearance (whiteness and gloss) is added, and a method for manufacturing a coated steel sheet using the same.

일반적으로 강판의 내식성을 향상하기 위하여 보편적으로 아연전기도금이 실시되고 있으며 아연전기도금 강판은 가전, 자동차, 건설 등등의 분야에 널리 사용되고 있다.In general, zinc electroplating is generally applied to improve the corrosion resistance of steel sheet, and zinc electroplated steel sheet is widely used in fields of home appliance, automobile, construction, and the like.

그러나 가혹한 분위기하에서 내식성을 확보하기 위하여 아연 도금층의 두께를 증가시켜야 하며 이로 인하여 비용이 증가하고 도금밀착성, 가공성, 용접성, 도장성 등의 품질 특성도 저하된다.However, in order to secure corrosion resistance in a severe atmosphere, the thickness of the zinc plated layer must be increased, resulting in an increase in cost and deterioration of quality characteristics such as plating adhesion, workability, weldability and paintability.

따라서 이러한 문제점을 개선하기 위해서 자동차용 강판을 중심으로 아연계 합금전기도금이 개발되었으며, 이중에 아연-철 합금전기도금재는 내식성, 가공성, 도장성등이 우수한 도금계로서 알려져 있다.In order to solve these problems, electroplating of zinc-based alloy has been developed mainly for automotive steel sheet, and zinc-iron alloy electroplating material is known as a plating system excellent in corrosion resistance, workability, and paintability.

여기서 아연-철 도금 방법은 도금욕의 성분에 따라서 여러가지가 제안되어 있으나, 그중 산성욕을 기본으로한 도금액이 일반적으로 많이 사용되고 있고, 산성 도금액은 황화물욕과 염화물욕을 구분할 수 있다.Various methods have been proposed for the zinc-iron plating method depending on the composition of the plating bath. Among them, a plating solution based on an acidic bath is generally used, and the acid plating solution can distinguish a sulfide bath from a chloride bath.

이때 염화물욕은 황화물욕에 비하여 전기 전도도가 우수하여 고전류밀도도금이 가능하고, 주로 용해성 양극을 사용하여 불용성 양극을 사용하는 황화물욕에 비하여 용액의 관리가 용이하고 비용이 적게 든다.In this case, the chloride bath is superior in electric conductivity to the sulfide bath, so that high current density plating is possible, and the solution is easier to manage and less expensive than a sulfide bath using an insoluble anode mainly using a soluble anode.

그러나 용해성 양극을 사용하는 염화물욕의 아연-철 합금전기도금 제품은 표면외관의 백색도 및 광택도 등이 불량하고, 표면이 거칠며, 목적 함량의 철 석출율이 낮으므로, 종래에는 아연-철 합금 전기도금에서의 철 석출률 및 표면조도를 향상시키기 위하여 미국특허 4772362에서와 같이 포리옥산알킬화합물을 이용하였으나 표면외관이 저하되었다.However, zinc-iron alloy electroplating products of chloride baths using soluble anodes are poor in whiteness and glossiness of surface appearance, have a rough surface, and have a low iron precipitation ratio of a desired content. Thus, conventionally, zinc- In order to improve the iron precipitation rate and surface roughness in the plating, although the polyoxy alkyl compound was used as in US Pat. No. 4,772,362, the surface appearance was degraded.

따라서 표면외관 개선을 위해서 일본특허 소64-47893은 첨가제로서 치환 포리에테러유 등을 첨가하여 표면균일 및 외관색조 등을 개선하였으나, 도금층의 표면이 거칠어지고, 철석출률이 증가되지 못하고, 일본특허 소64-47892에서는 비이온성 계면활성제인 폴리에틸렌글리콜의 첨가에 의하여, 내수밀착성, 화성처리성, 상층 철함유율 등을 개선하였으나 표면외관이 불량해지는 결점이 있다.Therefore, in order to improve the appearance of the surface, Japanese Patent No. 64-47893 improves the surface uniformity and appearance color tone by adding substituted polyether ether as an additive. However, the surface of the plating layer is roughened and the iron deposition rate is not increased, In Patent No. 64-47892, the addition of polyethylene glycol, which is a nonionic surfactant, improves water resistance, chemical conversion treatment, and iron content in the upper layer, but has the drawback that the surface appearance is poor.

본 발명은 상기한 문제점을 해결하여 아연-철 합금전기도금의 광택도 및 표면조도가 우수하고, 철 석출률이 증가하는 첨가제가 첨가된 아연-철 합금전기도금용의 용액 및 이를 이용한 도금강판 제조방법을 제공하는데 그 목적이 있다.The present invention solves the above problems and provides a zinc-iron alloy electroplating solution to which an additive having an excellent degree of gloss and surface roughness and an iron precipitation rate is added, and a coated steel sheet using the zinc-iron alloy electroplating The purpose of the method is to provide.

또한 본 고안은 첨가제가 첨가된 아연-철 합금전기도금용 용액을 pH 1. 0-5.0, 온도 40-70℃, 전류밀도 20-200A/㎠로 제한하고, 상기 아연-철 합금전기도금용 용액과 음극의 상대 유속을 0.5-2.5m/sec로 하여 전기도금하는 것을 특징으로 하는 첨가제가 첨가된 아연-철 합금전기도금용 용액을 이용하는 도금강판 제조방법을 제공한다.The present invention also provides a zinc-iron alloy electroplating solution to which an additive is added is limited to a pH of 1.0-5.0, a temperature of 40-70 ° C, and a current density of 20-200A / And the cathode is electroplated at a relative flow rate of 0.5 to 2.5 m / sec. The present invention also provides a method for producing a coated steel sheet using the zinc-iron alloy electroplating solution to which an additive is added.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

먼저 도금용액의 아연이온은 몰농도 0.8몰/리터 이하에서는 피복될 이온의 농도 부족에 의해서 도금에 검게 그을리는 자국(burning)을 일으키고, 2.5몰/리터 이상에서는 도금층이 분말 형태의 도금이 되어서 밀착성이 떨어지고 도금층의 철함량이 저하되어 내식성이 떨어진다.First, zinc ions in the plating solution cause burning in the plating due to insufficient concentration of the ions to be coated at a molar concentration of 0.8 mol / liter or less. When the amount exceeds 2.5 mol / liter, the plating layer becomes a powder- The adhesion is deteriorated and the iron content of the plating layer is lowered and the corrosion resistance is lowered.

또한 철이온의 몰농도가 0.1몰/리터 이하에서 도금층의 철함량이 감소하여 용접성 및 도장성이 열화되며, 몰농도 0.5몰/리터 이상에서는 도금층의 철함량이 너무높아 가공성이 저하되고, 갤버니부식(Galvanic Corrosion)에 의한 내식성이 저하된다.When the molar concentration of iron ions is less than 0.1 mol / liter, the iron content of the plating layer is decreased to deteriorate the weldability and paintability. When the molar concentration is more than 0.5 mol / liter, the iron content of the plating layer is too high, The corrosion resistance by the galvanic corrosion is lowered.

그리고 염소이온은 5.0몰/리터 이하에서 전기전도도의 감소로 인하여 버닝이 다량 발생되고, 9.0몰/리터 이상에서 용해도 문제로 염소이온이 석출되어 도금 작업성이 저하되며, 도금액 농도 관리가 어렵게 된다.When the concentration of chlorine ions is less than 5.0 moles / liter, burning occurs in a large amount due to a decrease in electric conductivity. When 9.0 mole / liter or more is used, chlorine ions are precipitated due to solubility problems, resulting in deterioration of plating workability and difficulty in plating solution concentration control.

이때 아연-철 합금전기도금은 도금층의 철함량이 5-30% 범위에서 내식성 및 가공성이 우수한데 바람직한 범위는 10-20%이다.At this time, zinc-iron alloy electroplating is excellent in corrosion resistance and processability in the range of iron content of plating layer of 5-30%, and preferable range is 10-20%.

따라서 철이온 : (철이온+아연이온) 비가 0.08 이하에서는 도금중 철함량이 5% 이하로 낮아지고, 0.3이상에서는 철함량이 30% 이상으로서 내식성 및 가공성이 불량하게 된다.Therefore, when the ratio of iron ion: (iron ion plus zinc ion) is less than 0.08, the iron content in the plating is lowered to 5% or less, and when 0.3 or more, the iron content is 30% or more.

한편 도금용액의 온도가 40℃ 이하에서는 도금층의 색상이 어둡고 도금층의 밀착성이 떨어져서 박리현상이 나타나며, 도금층의 철 함량도 저하되는 경향을 보이게 된다.On the other hand, when the temperature of the plating solution is below 40 캜, the hue of the plating layer becomes dark and the adhesion of the plating layer becomes poor, and the peeling phenomenon appears, and the iron content of the plating layer also tends to decrease.

또한 도금층의 온도가 70℃ 이상이 되면 도금 줄무늬가 발생하게 되며, 도금액의 증발이 심하여 작업 환경을 저해하고 아연 양극의 슬러지 발생이 심해지므로 도금액의 온도를 40℃에서 70℃범위로 제한하는게 바람직하다.Also, when the temperature of the plating layer is 70 ° C or higher, plating stripes are generated, the plating liquid evaporates too much and the working environment is hindered and the sludge generation of the zinc anode becomes severe, so that the temperature of the plating liquid is preferably limited to 40 ° C to 70 ° C .

그리고 도금용액의 pH는 1.0 이하에서는 도금표면이 어둡고 반광택 상태가 되며, 5.0이상에서는 도금 표면이 거칠어지고 도금액 중에 수산화철의 침전이 발생하므로 도금액의 pH는 1.0-5.0로 제한하는게 바람직하다.If the pH of the plating solution is less than 1.0, the plating surface becomes dark and semi-glossy. If the plating solution is 5.0 or more, the surface of the plating becomes rough and precipitation of iron hydroxide occurs in the plating solution. Therefore, the pH of the plating solution is preferably limited to 1.0-5.0.

또한 도금용액에서 전류밀도는 20A/d㎡에서 도금속도가 느려서 생산성이 떨어져 비용이 상승되며, 도금층의 철함량도 감소하게 되고, 200A/d㎡이상에서 금속이온의 확산속도의 제한으로 인하여 버닝발생 등 정상적인 도금 품질을 얻기 어려우므로 전류밀도는 40-200A/d㎡으로 제한하는 것이 필요하다.In addition, the current density in the plating solution is low at 20 A / dm 2, resulting in a low productivity and cost of the plating layer. Also, the amount of iron in the plating layer is decreased. At 200 A / dm 2 or more, , It is necessary to limit the current density to 40-200 A / dm 2.

한편 도금용액에서 도금용액과 음극의 상대유속이 0.5m/sec 이하에서는 금속이온의 확산속도가 제한되므로 고전류밀도 도금을 어렵게 하며, 2.5m/sec이상의 유속을 얻는다는 것은 설비상으로 어렵기 때문에 유속의 범위는 0.5-2.5m/sec로 한정하는게 바람직하다.On the other hand, when the relative velocity between the plating solution and the cathode in the plating solution is less than 0.5 m / sec, the diffusion rate of the metal ions is limited, making it difficult to coat the high current density and obtaining a flow rate of more than 2.5 m / Is preferably limited to 0.5-2.5 m / sec.

상기 도금용액에서 첨가제로서 폴리에틸렌글리콜 n의 수가 10 이하에서는 도금 결정립의 미세화 효과가 미약하여 조도가 불량하며, n의 수가 30이상인 것을 사용하면 도금층의 표면외관 향상 효과가 감소된다.When the number of the polyethylene glycol n as the additive in the plating solution is 10 or less, the fineness of plating crystal grains is weak and the roughness is poor. When the number of n is 30 or more, the effect of improving the surface appearance of the plating layer is reduced.

여기서 n의 수가 10에서 20사이의 성분과 20에서 30이상의 성분의 비율은 1:2에서 1:5 범위로 한정한 것은 n수의 하한과 상한을 설정한 이유와 동일하며, n수가 많은 성분은 표면외관 향상 기능을 나타낸다.Here, the ratio of the component having the number of n of 10 to 20 and the component of 20 to 30 or more is limited to the range of 1: 2 to 1: 5, which is the same as the reason of setting the lower limit and the upper limit of the number n, Surface appearance enhancement function.

이들 혼합물의 수용액중 농도가 10퍼센트 이하에서는 도금 결정의 미세화 효과가 적어서 표면이 거칠게 되고, 15퍼센트 이상이 되면 도금층의 표면외관 및 철석출률 향상 효과가 감소하게 된다.When the concentration of such a mixture in the aqueous solution is less than 10 percent, the surface fineness of the plating crystal becomes small, and when the concentration exceeds 15 percent, the surface appearance of the plating layer and the effect of improving the iron deposition rate are reduced.

또한 방향족산은 0.1%이하에서 입자가 균일하지 못하고, 5%이상에서 도금층에 노란줄무늬가 발생되며, 도금상태도 불량하게 된다.In addition, when the aromatic acid content is less than 0.1%, the particles are not uniform, and when more than 5%, yellow stripes are formed on the plating layer and the plating state is also poor.

더욱이 프로파질알콜 0.01% 이하에서는 표면외관이 향상되지 못하고, 도금층의 철 석출률이 증가되지 못하며, 1.00% 이상에서는 전류효율이 열악해져서 도금층에 버닝이 발생된다.Further, when the content of the propanol alcohol is less than 0.01%, the surface appearance is not improved and the iron deposition rate of the plating layer is not increased. When the content exceeds 1.00%, the current efficiency becomes poor and burning occurs in the plating layer.

이상과 같이 제조된 첨가제의 도금욕 첨가량이 0.5ml/l이하에서는 도금결정립 미세화에 의한 조도, 표면외관 및 석출률 향상 효과를 얻을수 없으며, 6.0㎖/ℓ 이상 함유되면 광택도가 오히려 저하되고 도금전류의 효율이 낮아지는 현상이 나타난다.When the amount of the additive prepared as described above is less than 0.5 ml / l, the effect of improving the surface roughness, surface appearance and precipitation ratio due to refinement of the plating crystal grains can not be obtained. Is lowered.

이상에서 언급된 바와같은 범위의 첨가제를 아연-철 합금 전기도금을 행할시 산성 염화물욕에 첨가하면 도금 결정립이 미세 균일하고 광택도가 우수한 특성을 나타낸다.When the additive in the range mentioned above is added to the acidic chloride bath when performing the zinc-iron alloy electroplating, the plating crystal grains exhibit fine uniformity and excellent glossiness.

본 발명의 첨가제는 피도금체의 금속 종류, 형상에 관계없이 산성 염화물을 이용하는 아연-철 합금 전기도금에 적용될 수 있으며, 특히 고전류 밀도도금이 필요한 강판의 연속 전기 아연도금시 우수한 도금품질을 용이 하게 얻을 수 있는 매우 유효한 수단이 된다.The additive of the present invention can be applied to zinc-iron alloy electroplating using an acid chloride regardless of the kind and shape of the metal to be plated, and in particular, it can easily provide excellent plating quality in galvanizing of continuous steel sheet requiring high current density plating It becomes a very effective means to get.

이하 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail by way of examples.

(실시예)(Example)

냉연 강판을 소지금속으로 하여 하기 표1에 나타낸 도금액 조성에서 도금조건에 따라서 도금량이 40g/d㎡이 되게 도금하였을때 도금층의 백색도, 광택도, 조도, 철 석출물(도금층 철 함량/도금액 철 함량)을 나타낸 것이다.When the cold-rolled steel sheet was plated to a plating amount of 40 g / dm 2 according to the plating conditions in the plating solution composition shown in Table 1 below, whiteness, gloss, roughness, iron precipitate (iron content in the plating layer / iron content in the plating solution) Lt; / RTI >

[표 1][Table 1]

도금용액에 첨가제에 따른 표면 백색도, 광택도, 조도, 철 석출물(도금층 철함량/도금액 철함량) 여기서 pH=2, 온도=60℃, 상대유속=1.5m/sec, 전류밀도=60A/d㎡으로 설정하였다.The surface brightness, gloss, roughness and iron precipitate (plating layer iron content / plating solution iron content) according to the additive in the plating solution were pH = 2, temperature = 60 캜, relative flow rate = 1.5 m / Respectively.

* 백색도 : Color Dilference Meter의 L값(양호: 66이상, 보통: 58-68, 불량 : 58이하)* Whiteness: L value of Color Dilference Meter (Good: 66 or more, Normal: 58-68, Bad: 58 or less)

** 광택도 : gloss Meter(양호 : 60이상, 보통: 40-60, 불량 : 40이상)** Gloss: gloss Meter (good: over 60, medium: 40-60, bad: over 40)

** 조도 : 도금제조도(Rmax)-원판조도(Rmax) (양호: 1um이하, 보통: 1-2um, 불량: 2um 이상)** Roughness: Plating Manufacture (Rmax) - Roughness (Rmax) (Good: Less than 1um, Medium: 1-2um, Bad: More than 2um)

*** 철석출률(양호: 0.9이상, 보통: 0.8-0.9, 불량: 0.8이하)*** Iron precipitation rate (good: 0.9 or more, average: 0.8 to 0.9, poor: not more than 0.8)

상기 표1에 나타낸 바와 같이 본 발명에 부합되는 발명예(1-12)는 표면조도, 표면외관(광택도, 백색도)및 철석출률이 양호하지만, 발명의 범위를 벗어난 도금용액에서 실시된 비교예(13-25)에서는 표면조도, 표면외관 및 철석출률이 불량함을 알 수 있다.As shown in Table 1, the inventive examples (1-12) in accordance with the present invention are excellent in surface roughness, surface appearance (gloss, whiteness) and iron precipitation rate, In Example (13-25), the surface roughness, surface appearance and iron precipitation rate are poor.

상술한 바와 같이 본 발명은 아연-철의 합금전기도금에 있어서 염화물계의 도금액에서 도금층의 표면조도, 표면외관, 철석출물을 양호하게 하여 품질을 향상시켜는 효과를 제공한다.As described above, the present invention provides an effect of improving the surface quality, surface appearance, and iron precipitates of the plating layer in the chloride-based plating solution in zinc-iron alloy electroplating to improve quality.

Claims (2)

염화아연의 아연이온 몰농도: 0.8-2.0몰/리터, 염화철의 철이온의 몰농도: 0.15-0.5몰/리터, 염화이온의 몰농도: 5.0-9.0몰/리터, 철이온 : (아연이온+철이온)의 몰비가 0.08-0.3:1이 되도록 조성된 아연 -철 합금전기도금 용액에 있어서,Molar concentration of iron chloride: 0.15-0.5 mol / liter, molar concentration of chloride ion: 5.0-9.0 mol / liter, iron ion: zinc ion + zinc ion molar concentration: 0.8-2.0 mol / Iron ion is in the range of 0.08 to 0.3: 1, the zinc- 폴리에틸렌글리콜 {[H(COH2CH2)n]OH}의 중합도 n수가 10-20 범위와 20-30 범위인 것을 각각 1종 이상 혼합하여 그 혼합비가 중량비로 1:2-1:5인 혼합 폴리에티렌글리콜을 조성한 후, 상기 혼합 폴리에틸렌글리콜의 농도가 10-15%인 수용액에 방향족산과 푸로파질알콜을 상기 혼합 폴리에틸렌글리콜의 중량에 대하여 0.1-5.0중량% 및 0.01-1.0중량% 되도록 첨가하여 조성된 첨가제를 상기 아연-철 합금전기도금 용액에 0.5-6.0ml/L 농도로 첨가하는 것을 특징으로 하는 첨가제가 첨가된 아연-철 합금전기도금용 용액.A mixture of polyethylene glycol {[H (COH 2 CH 2 ) n ] OH} having a polymerization degree of n in the range of 10-20 and 20-30, respectively, in a weight ratio of 1: 2-1: 5 After adding poly (ethylene glycol), an aromatic acid and a fugitive alcohol were added to an aqueous solution having a concentration of 10-15% of the mixed polyethylene glycol so as to be 0.1-5.0 wt% and 0.01-1.0 wt% based on the weight of the mixed polyethylene glycol Wherein the added additive is added to the zinc-iron alloy electroplating solution at a concentration of 0.5-6.0 ml / L, and the additive is added to the zinc-iron alloy electroplating solution. 제 1항의 첨가제가 첨가된 아연-철 합금전기도금용 용액을 pH1.0-5.0, 온도 40-70℃, 전류밀도 20-200A/㎠로 제한하고, 상기 아연-철 합금전기도금용 용액과 음극의 상대유속을 0.5-2.5m/sec로 하여 전기도금하는 것을 특징으로 하는 첨가제가 첨가된 아연-철 합금전기도금용 용액을 이용하는 도금강판 제조방법.The zinc-iron alloy electroplating solution to which the additive of claim 1 is added is limited to a pH of 1.0-5.0, a temperature of 40-70 ° C, and a current density of 20-200 A / cm 2, Wherein the electroplating is performed at a relative flow rate of 0.5-2.5 m / sec. The method for producing a coated steel sheet using the additive-added zinc-iron alloy electroplating solution.
KR1019960019279A 1996-05-31 1996-05-31 ADDITIVE ADDED Zn-Fe ALLOY ELECTROPLATING SOLUTION AND METHOD FOR MANUFACTURING COATED STRIP USING THE SAME KR100370569B1 (en)

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