KR20030057243A - Manufacturing method of Zn-Ni electroplated steel sheet having a excellent chipping resistance by the addition of pickling accelerator - Google Patents

Manufacturing method of Zn-Ni electroplated steel sheet having a excellent chipping resistance by the addition of pickling accelerator Download PDF

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KR20030057243A
KR20030057243A KR1020010087645A KR20010087645A KR20030057243A KR 20030057243 A KR20030057243 A KR 20030057243A KR 1020010087645 A KR1020010087645 A KR 1020010087645A KR 20010087645 A KR20010087645 A KR 20010087645A KR 20030057243 A KR20030057243 A KR 20030057243A
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steel sheet
chipping resistance
pickling
hydrochloric acid
pickling accelerator
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KR1020010087645A
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KR100428025B1 (en
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이용진
전유택
정연수
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현대하이스코 주식회사
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

PURPOSE: A method for manufacturing Zn-Ni electroplated steel sheet having excellent chipping resistance by addition of pickling accelerator is provided, which is characterized in that micro roughness is formed along grain boundary of a substrate to be plated to increase adhesion property between the substrate and plating layer. CONSTITUTION: The method is characterized in that a pickling accelerator comprising gluconic acid 5 to 30 wt.%, hydrogen peroxide 5 to 40 wt.%, sodium phosphonate 3 to 15 wt.%, 5 wt.% or less of organic catalyst and a balance of water is added into a 12 % chloride solution in an amount of 0.5 to 10 vol.%, so that micro roughness is formed on steel sheet.

Description

산세촉진제 첨가에 의한 내칩핑성이 우수한 자동차용 Zn-Ni 전기도금강판의 제조방법 {Manufacturing method of Zn-Ni electroplated steel sheet having a excellent chipping resistance by the addition of pickling accelerator}Manufacturing method of Zn-Ni electroplated steel sheet having a excellent chipping resistance by the addition of pickling accelerator}

본 발명은 연속전기도금라인의 산세공정에서 사용되는 염산용액에 산세촉진제를 첨가함으로써 염산의 농도를 증가시키지 않고도 내칩핑성이 우수한 아연-니켈 합금도금강판 제조방법에 관한 것이다. 보다 상세하게는 산세공정에서 사용되는 염산용액에 산세촉진제를 첨가함으로 표면의 에칭 효과를 극대화시켜 표면에 미세한요철(凹凸)을 형성시켜 도금층과 소재와의 밀착력을 증가시킴으로써 내칩핑성이 우수한 Zn-Ni합금도금강판의 제조 방법에 관한 것을 그 요지로 한다.The present invention relates to a method for producing a zinc-nickel alloy plated steel sheet having excellent chipping resistance without increasing the concentration of hydrochloric acid by adding a pickling accelerator to a hydrochloric acid solution used in a pickling process of a continuous electroplating line. More specifically, by adding a pickling accelerator to the hydrochloric acid solution used in the pickling process, the etching effect of the surface is maximized to form fine concavities and convexities on the surface, thereby increasing the adhesion between the plating layer and the material. The summary relates to a method for producing a Ni alloy plated steel sheet.

최근, 자동차 차체의 방청성능에 대한 요구가 점차 증가하며 각 자동차사 및 강판제조 업계는 자동차 강판의 방청성능 향상을 위한 여러 가지 대책 마련에 부심하고 있다. 특히 냉한지를 중심으로 겨울철 도로 동결 방지용 염류를 대량으로 살포하기 때문에 이에 따른 차체 표면의 부식 문제가 대두되어 내식성이 우수한 합금전기도금 강판이 개발되어 자동차용 소재로 적용되고 있다. 종래의 전기아연도금 강판에서 내식성을 확보하기 위해서는 도금층의 부착량을 증가시켜야 하나 이는 곧 생산비용의 증가 및 원가상승을 유발시키며, 용접성, 가공성 등 제반 제조특성을 저하시킨다는 문제점들이 있다.Recently, the demand for the anti-rust performance of the automobile body is gradually increasing, each automobile company and the steel plate manufacturing industry is struggling to prepare a variety of measures to improve the anti-rust performance of the automotive steel sheet. In particular, since the spraying of salt for preventing freezing in winter roads in large quantities in the cold districts, the corrosion of the surface of the vehicle has been raised, and an alloy electroplating steel sheet having excellent corrosion resistance has been developed and applied to automobile materials. In order to secure corrosion resistance in the conventional galvanized steel sheet, it is necessary to increase the adhesion amount of the plating layer, which causes an increase in production cost and an increase in cost, and deteriorates all manufacturing characteristics such as weldability and workability.

따라서 아연도금강판보다 내식성이 우수한 아연-니켈 합금도금이 개발되어 아연도금강판을 대체하여 사용 중에 있으나, 저온에서 돌에 의한 충격으로 도금층이 박리되는 현상인 저온 내칩핑성과 도금층과 소재 사이의 밀착력이 취약하다는 단점을 가지고 있으므로 아연-니켈 도금층의 뛰어난 내식성을 이용하기 위해서는 이러한 소재와 도금층 간의 밀착력을 증가시킬 필요가 있으며 저온 내칩핑성에 대한 저항성을 갖는 도금층의 개발이 필요하다.Therefore, zinc-nickel alloy plating, which has better corrosion resistance than galvanized steel sheet, has been developed to replace galvanized steel sheet, but the low temperature chipping resistance and adhesion between the plating layer and the material, which is a phenomenon in which the plating layer is peeled off due to the impact of stone at low temperature, In order to take advantage of the excellent corrosion resistance of the zinc-nickel plated layer, it is necessary to increase the adhesion between the material and the plated layer and develop a plated layer having resistance to low temperature chipping resistance.

다른 표면처리강판들에 비해 아연-니켈 합금도금강판이 저온 내칩핑성이 약한 이유는 도금층이 금속간화합물인 감마()상으로 이루어져 있기 때문에 외부 응력에 의해 변형이 적어 균열발생이 용이하기 때문이다. 따라서 저온에서 돌에 의한 충격 시 도금층과 소재의 계면에서 박리가 발생한다.The reason why zinc-nickel alloy plated steel sheet has low chipping resistance is low compared to other surface-treated steel sheets. This is because cracks are easily formed due to the small deformation due to external stress. Therefore, peeling occurs at the interface between the plated layer and the material during impact by stones at low temperatures.

저온 내칩핑성을 향상시키는 방안으로는 이미 출원된 특허 제00-0075817호와 특허 제00-0075818호에서 도금층내 Ni 함량을 경사도금 해주는 방법과 하지층으로 아연도금을 행해주는 두 가지 방법이 제안되었다. 이 두 방법은 주로 하지층과 도금층 계면의 특성을 변화시켜주는데 그 목적이 있다. 즉 계면에서 초기에 형성되는 도금층의 경도를 낮게 해 줌으로써 외부충격에 의한 응력이 완충작용을 할 수 있도록 해 주었다.As a method of improving low temperature chipping resistance, two methods of gradient plating of Ni content in the plating layer and zinc plating of the underlying layer are proposed in patent applications 00-0075817 and 00-0075818. It became. These two methods mainly aim to change the characteristics of the interface between the base layer and the plating layer. In other words, by lowering the hardness of the plating layer initially formed at the interface, the stress caused by external impact can be buffered.

본 발명에서는 상기에 서술했던 내칩핑성 문제를 해결하기 위하여 연속전기도금 공정 중 산세공정에서 염산 산세액 중에 첨가제를 사용하여 소재 표면이 과에칭되어 미세한 미소조도를 형성시켜 줌으로 해서 도금층과 소재와의 밀착력을 향상 시킴으로써 저온에서도 내칩핑성이 우수한 아연-니켈 합금도금강판을 제조하는 방법을 제공하고자 하였다.In the present invention, in order to solve the chipping resistance problem described above, the surface of the material is overetched by using an additive in the hydrochloric acid pickling solution in the pickling process of the continuous electroplating process to form fine fine roughness. It was to provide a method of manufacturing a zinc-nickel alloy plated steel sheet having excellent chipping resistance even at low temperature by improving the adhesion of the.

소재 표면을 에칭시켜 미세한 미소조도를 형성시켜 주는 방법으로는 종래의 경우 염산농도를 15% 이상으로 증가시켜주는 방법들이 제안되었다.As a method of forming fine microroughness by etching the surface of the material, methods of increasing hydrochloric acid concentration to 15% or more have been proposed in the related art.

또한, 최초 도금 2 ~ 5g/m2정도로 한 후 염산 용액에 다시 에칭시켜 강판표면에 미세조도를 부여하고 그 위에 최종 20g/m2정도로 도금하여 내칩핑성을 개선하도록 한 방법들이 제한된 바 있으나, 후자의 경우에는 생산성에 문제가 있으며, 또한 공정이 번거롭고 염산농도를 증가시켜 주게 되면 염산이 비산되어 주위 설비를 부식시키는 문제점을 유발시키며 산세 탱크의 유지 관리 및 보수가 어렵고 또한 작업자에게 열악한 환경을 제공한다는 문제점을 야기시킨다. 따라서 낮은 염산농도에서 산세촉진제를 첨가함으로써 염산을 증가시켰을 때와 마찬가지로 표면에 미소조도를 형성시켜 내칩핑성 개선효과가 보다 크도록 하였다.In addition, the first plating is about 2 ~ 5g / m 2 After etching to the hydrochloric acid solution to give a fine roughness on the surface of the steel sheet and the final 20g / m 2 on the plating to improve the chipping resistance has been limited, In the latter case, productivity is a problem, and if the process is cumbersome and increases the concentration of hydrochloric acid, hydrochloric acid is scattered causing corrosion of surrounding equipment, and it is difficult to maintain and repair the pickling tank and provide a poor environment for the workers. Cause problems. Therefore, as the hydrochloric acid was increased by adding an acid pickling accelerator at low hydrochloric acid concentration, microroughness was formed on the surface to improve the chipping resistance.

발명의 목적을 달성하기 위해서는 산세공정에서 약 12% 이하의 염산 용액에 글루콘산, 과산화수소, 유기촉매제, 기타 산등으로 구성된 산세촉진제를 첨가해 줌으로써 소재표면의 결정입계 및 입내에 미세한 미소조도를 부여해 줌으로써 염산농도를 15% 이상 증가시켜 주는 경우보다 일층 조도가 균일하고 과부식을 방지하여 내칩핑성이 우수한 아연-니켈 합금전기도금강판의 제조방법에 관한 것을 그 요지로 한다.In order to achieve the object of the invention, in the pickling process, pickling accelerators composed of gluconic acid, hydrogen peroxide, organic catalysts, and other acids are added to hydrochloric acid solution of about 12% or less to impart crystal grain boundaries of the surface of the material and fine micro-roughness in the mouth. The gist of the present invention relates to a method of manufacturing a zinc-nickel alloy electroplated steel sheet having a uniform roughness and preventing overcorrosion and having excellent chipping resistance than increasing the concentration of hydrochloric acid by 15% or more.

본 발명에서는 상기에 서술했던 산세공정에서 염산용액에 클루콘산, 과산화수소, 유기촉매제, 기타 산등으로 구성된 산세촉진제를 첨가해 주어 과에칭에 의한 미소조도를 부여함으로써 내칩핑성이 우수한 아연-니켈 합금전기아연도금강판의 제조방법을 제공하는데 그 목적이 있다.In the present invention, in the pickling process described above, a pickling accelerator composed of gluconic acid, hydrogen peroxide, an organic catalyst, and other acids is added to the hydrochloric acid solution to give a fine roughness by over-etching, thereby providing zinc-nickel alloy with excellent chipping resistance. Its purpose is to provide a method for producing galvanized steel sheet.

이러한 목적을 달성하기 위하여 본 발명에서는 상온의 염산용액에 산세촉진제를 최소한 0.5% 이상 첨가하여 표면의 결정입계와 결정입내에서 미소조도를 형성시켜 내칩핑성이 우수한 아연-니켈 합금전기도금강판을 제조하는 것을 특징으로 한다.In order to achieve this purpose, in the present invention, a pickling accelerator is added to a hydrochloric acid solution at room temperature to at least 0.5% to form a fine roughness in the grain boundaries and grains of the surface to prepare a zinc-nickel alloy electroplating steel sheet having excellent chipping resistance. Characterized in that.

제 1 도 본 발명은 산세촉진제 농도에 따른 소재 표면의 광택도 변화도이다.1 is a change in glossiness of the surface of the material according to the concentration of pickling accelerators.

제 2 도 본 발명은 산세촉진제 첨가량에 따른 소재 표면의 미세구조 사진이다.2 is a microstructure photograph of a material surface according to the amount of pickling accelerator added.

제 3 도 본 발명은 산세촉진제 농도에 따른 소재 및 도금층 표면의 광택도 변화도이다.3 is a glossiness change diagram of the surface of the material and the plating layer according to the concentration of pickling accelerators.

제 4 도 염산농도 변화에 따른 내칩핑성의 변화를 나타낸 그림이다.4 is a graph showing the change in chipping resistance according to the hydrochloric acid concentration.

제 5 도 본 발명은 산세촉진제 첨가량과 내칩핑성과의 상관관계도이다.5 is a correlation diagram of pickling accelerator addition amount and chipping resistance.

상술한 바의 목적을 달성하기 위하여 본 발명은 연속전기도금라인에서 내칩핑성을 향상시키기로 하고 이를 위하여 산세공정에서 상온의 염산용액에 산세촉진제를 0.5% 이상 10% 이하로 첨가하여 영하의 저온에서도 내칩핑성이 우수한 자동차용 아연-니켈 합금전기도금강판의 제조방법을 제공하는 것을 특징으로 한다.In order to achieve the object described above, the present invention is to improve the chipping resistance in the continuous electroplating line and to this end, the pickling accelerator is added to the hydrochloric acid solution at room temperature in the pickling process at 0.5% or more to 10% or less even at low temperatures below zero. It is characterized by providing a manufacturing method of zinc-nickel alloy electroplating steel sheet for automobiles excellent in chipping resistance.

여기에서, 산세촉진제로서는 중량대비 글루콘산 5-30%, 과산화수소 5-40%, 인산나트륨 3-15%, 유기촉매제 5%이하, 나머지 물로 구성된 것을 산세용액인 농도 12%이하의 염산용액에 부피비율로 0.5-10% 첨가한 것을 본 발명상의 산세촉진제로 한다.Here, the pickling accelerator is composed of 5-30% of gluconic acid, 5-40% of hydrogen peroxide, 3-15% of sodium phosphate, 5% or less of an organic catalyst, and the remaining water in a hydrochloric acid solution having a concentration of 12% or less of a pickling solution. The addition rate of 0.5-10% is used as the pickling accelerator of the present invention.

여기에서, 산세촉진제 첨가량 10%를 상한으로 한 이유는The reason why the amount of acid pickling accelerator added is 10% is the upper limit.

산세촉진제를 첨가하면 그 양이 증가함에 따라 표면이 그에 비례하여 에칭되지만 그 첨가량이 10%이상 되면 결정입계 및 결정입내에서 형성되는 미세조도의 형상이 V자형으로 되기 때문에 그 효과가 거의 없으며 또한 표면의 지나친 에칭으로 인해 표면이 충분한 기계적 성질을 가질 수 없는데다 그 위에 도금층이 형성되면 도금층과 소재간에 밀착력이 증가하여도 표면층의 기계적 성질이 약화되기 때문에 10 %이하로 제한한다. 즉 에칭에 의하여 표면의 미세조도 형상을 V자 형태가 아닌 凹 형태로 만들어 주어야지만 그 효과 크게 된다.When the pickling accelerator is added, the surface is etched proportionally as the amount is increased, but when the addition amount is more than 10%, the grain roughness and the fine roughness formed in the grain become V-shaped, and the effect is almost insignificant. Due to excessive etching, the surface may not have sufficient mechanical properties, and if the plating layer is formed thereon, the mechanical properties of the surface layer are weakened even if the adhesion between the plating layer and the material is limited to 10% or less. In other words, the surface roughness should be made into the shape of the fin rather than the V shape by the etching, but the effect is large.

또한, 여기에서 글루콘산(gluconic acid)은 용해도를 좋게하고 광택도를 향상시키는 요소로, 5% 이상에서 효과를 나타내나 30%를 초과하면 오히려 에칭효과를 저하시킨다. 또한 과산화수소는 (H2O2)5%이상에서 청정효과를 발휘하고 속히 에칭효과를 가져다 주는 역할을 하나, 그 분해과정에서 산소(O2)를 방출하므로 강표면에서 강력한 산화를 폭발적으로 촉진하므로 40%이상 초과하여 첨가되면 지나치게 과에칭되고, 빠른 시간내에 부식효과를 촉진하므로 에칭제어가 어렵다. 인산나트륨은 3% 이상에서 강알카리성을 유지하여 산화촉진속도를 조절하고, 15% 이상 첨가시 오히려 산화촉진을 위한 에칭효과를 저해한다.In addition, the gluconic acid (gluconic acid) is a factor that improves the solubility and improve the gloss, it shows an effect at 5% or more, but exceeds 30% rather reduces the etching effect. In addition, hydrogen peroxide plays a role of cleaning effect and quick etching effect in more than 5% of (H 2 O 2 ), but it releases oxygen (O 2 ) in the process of decomposition, explosively promoting strong oxidation on steel surface. If it is added in excess of 40%, it is excessively etched and promotes the corrosion effect in a short time, so that etching control is difficult. Sodium phosphate maintains the strong alkalinity at 3% or more to control the oxidation acceleration rate, and when added more than 15% rather inhibits the etching effect for the oxidation promotion.

도 1 은 상온의 염산용액에 산세촉진제를 첨가하였을 때 강판의 표면 광택도 변화를 나타낸 것이다. 광택도는 광택도계(Tri-Microgloss-60-85)를 이용하여 입사각 60°에서 측정하였다. 산세촉진제의 첨가량이 증가함에 도금 소재의 광택도는 대략 산세촉진제농도 3% ~ 5% 까지는 급격히 감소하고 그 이상부터는 서서히 감소함을 알 수 있다.Figure 1 shows the change in the surface gloss of the steel sheet when the pickling accelerator is added to the hydrochloric acid solution at room temperature. Glossiness was measured at an incident angle of 60 ° using a glossmeter (Tri-Microgloss-60-85). As the amount of pickling accelerator is increased, the glossiness of the plating material decreases rapidly from about 3% to 5% of pickling accelerator concentration, and gradually decreases from thereafter.

이는 염산용액 및 산세촉진제에 의한 과에칭이 발생하면 표면에 미세한 미소조도(Micro-roughness)가 형성되어 광택도가 저하되기 때문이다.This is because over-etching by the hydrochloric acid solution and the pickling accelerator generates fine micro-roughness on the surface, thereby decreasing gloss.

도 2 는 산세촉진제 첨가에 따른 표면의 미세구조 변화를 사진으로 나타낸 것이다. 산세촉진제는 약 0.5%만 첨가되어도 입내 및 입계에서 미소조도가 형성되고 있음을 알 수 있다.2 is a photograph showing the microstructure change of the surface according to the addition of the pickling accelerator. It can be seen that even when only about 0.5% of the pickling accelerator is added, microroughness is formed in the mouth and grain boundaries.

도 3은 산세촉진제를 사용하였을 때의 도금소재와 도금 후의 광택도 변화를 나타낸 것이다. 도 1에서 산세촉진제 첨가량이 증가함에 따라 광택도가 현저히 감소하였는데 도3을 살펴보면 도금층의 광택도 변화는 거의 없었음을 알 수 있다. 이는 도금소재 표면에 미세하게 형성되었던 미소조도가 도금되며 채워지고 최종 도금후에는 표면외관 특성이 동일해지기 때문이다. 그러면서도 도금층과 소재간의 밀착력이 증대되어 내칩핑성이 개선될 수 있게 된다. 따라서 아연-니켈 도금층이 우수한 내칩핑성을 갖기 위해서는 소재표면에 미세조도가 형성되어야 함을 알 수 있다.Figure 3 shows the change in the gloss after plating and plating material when the pickling accelerator is used. As the amount of pickling accelerator added in FIG. 1 increased, the glossiness was remarkably decreased. Referring to FIG. 3, the glossiness of the plated layer was hardly changed. This is because the fine roughness formed on the surface of the plating material is plated and filled, and the surface appearance characteristics are the same after the final plating. At the same time, adhesion between the plating layer and the material is increased, thereby improving chipping resistance. Therefore, it can be seen that in order for the zinc-nickel plating layer to have excellent chipping resistance, fine roughness should be formed on the surface of the material.

상술한 본 발명상의 미소조도를 갖는 강판의 표면은 그 에칭 부분으로 인해 凹 면을 형성하는 것이 특징이다.The surface of the steel sheet having the microroughness of the present invention described above is characterized by forming a concave surface due to the etching portion.

유기촉매제로서는 통상의 유기촉매제를 사용하는데, 이는 광택도를 유지하고 밀착성을 향상시키기 위한 것으로, 그러나 5%를 초과하면 에칭효과를 저해하는 것으로 나타났다.As the organic catalyst, a conventional organic catalyst is used, which is intended to maintain gloss and improve adhesion, but when it exceeds 5%, it has been shown to inhibit the etching effect.

이하 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.The present invention will be described in more detail with reference to the following Examples.

[실시예]EXAMPLE

두께 0.6 ~ 0.8mm의 일반 저탄소 냉연강판을 사용하여 다음과 같은 조건 하에서 아연-니켈 합금전기도금을 행하였다. 산세촉진제 첨가 효과를 알아보기 위하여 도금 전 염산농도를 8 ~ 20% 범위에서 변화시켰으며 각각의 경우에 산세촉진제 첨가량을 변화시켜 산세를 행하였다.Zinc-nickel alloy electroplating was carried out using a general low carbon cold rolled steel sheet having a thickness of 0.6 to 0.8 mm under the following conditions. In order to examine the effect of the pickling accelerator, the concentration of hydrochloric acid was changed in the range of 8 to 20% before plating, and in each case, the pickling was performed by changing the addition amount of the pickling accelerator.

냉연강판 도금액으로는 황산욕을 사용하여 도금액 온도 50 ~ 65℃, pH 1.4 ~ 2.0, 유속 2m/sec의 조건하에 부착량이 20g/m2이 되도록 행하였다.As a cold-rolled steel plate plating solution, a sulfuric acid bath was used so that the deposition amount might be 20 g / m 2 under the conditions of a plating solution temperature of 50-65 degreeC, pH 1.4-2.0, and a flow rate of 2 m / sec.

각 시편들에 대한 내칩핑 시험은 -20℃에서 2.5 ~ 5.0 mm크기의 비석 50g을 사용하여 4kgf/cm2의 압력으로 시편 표면에 충돌시켜 각각의 박리면적들에 대하여 가장 넓게 박리된 부위의 길이를 측정하여 다음과 같은 기준에 의하여 평가하였다. 그리고 각각의 박리면적들에 대하여 총합을 구하여 칩핑저항성을 평가하였다.The chipping test for each specimen was carried out using 50 g of 2.5 to 5.0 mm sized stone at -20 ° C, impinging on the surface of the specimen at a pressure of 4 kgf / cm 2 , the length of the most peeled area for each peeled area. Was measured and evaluated according to the following criteria. In addition, the chipping resistance was evaluated by totaling the respective peeling areas.

[표 1]TABLE 1

상기의 실시예로부터 평가된 주요결과와 효과에 대하여 설명하면 다음과 같다.Referring to the main results and the effects evaluated from the above embodiment are as follows.

도 4 는 염산용액의 농도 변화에 따른 칩핑시험결과도이며 도 5는 산세촉진제 첨가량에 따른 칩핑시험결과도이다. 여기에서 염산농도가 증가함에 따라 칩핑저항성이 저하되나 다만, 약 13% 이상에서는 칩핑 저항성이 약 30% 정도 개선된다.4 is a chipping test result diagram according to the concentration change of the hydrochloric acid solution, and FIG. 5 is a chipping test result diagram according to the addition amount of the pickling accelerator. Here, the chipping resistance is lowered as the concentration of hydrochloric acid is increased, but the chipping resistance is improved by about 30% at about 13% or more.

그러나 염산농도의 증가는 앞서 기술했던 바와 같이 산세용액의 비산에 따른 주위 설비부식 문제와 작업자에게 열악한 작업환경을 제공한다는 단점이 있다. 특히 염산농도가 12%를 초과하거나 산세촉진제 첨가량이 염산용액 대비 10%초과할 정도로 너무 많아지면 표면의 에칭정도가 심해지며 결정입계가 V자 형태로 미소조도가 형성되는 일이 확인되었고, 凹 형태로 형성될 때보다 도금층과 소재간의 밀착력이 떨어져 칩핑저항성 개선효과가 나빠져 바람직하지 않다. 따라서 염산농도는 12% 이하로 하였다.However, the increase in hydrochloric acid concentration, as described above, has the disadvantages of corrosion of the surrounding equipment due to the scattering of pickling solution and providing a poor working environment for workers. In particular, when the concentration of hydrochloric acid exceeds 12% or the amount of the pickling accelerator is more than 10% higher than that of the hydrochloric acid solution, the degree of etching on the surface is increased, and the grain boundary has a V-shape to form fine roughness. The adhesion between the plated layer and the material is lower than that of the semiconductor layer, so that the effect of improving chipping resistance is deteriorated. Therefore, the concentration of hydrochloric acid was made 12% or less.

상술한 바와 같이 염산농도를 12%이하로 하더라도 이에 관계없이 산세촉진제를 사용할 경우 염산농도가 증가할 때와 마찬가지로 내칩핑성이 현저히 개선되며 그 효과가 매우 큼을 도 5 로 알 수 있다.As described above, even if the hydrochloric acid concentration is 12% or less, the use of an acid pickling accelerator may significantly improve the chipping resistance and increase the effect as shown in FIG.

상술한 바와 같이 본 발명에서는 산세공정에서 염산용액에 클루콘산, 과산화수소, 유기촉매제, 기타 산등으로 구성된 산세촉진제를 0.5 ~ 10%로 첨가해 주어 과에칭에 의해 결정입계 및 입내에 미소조도를 부여함으로써 도금층과 소재간에 밀착력을 증대시켜 내칩핑성이 대략 30% 이상 개선된 우수한 내칩핑성을 갖는 아연-니켈 합금전기아연도금강판을 제조할 수 있었다.As described above, in the present invention, an acid pickling accelerator composed of gluconic acid, hydrogen peroxide, an organic catalyst, and other acids is added to the hydrochloric acid solution in the pickling process at 0.5 to 10% to give grain boundary and fine roughness in the mouth by overetching. By increasing the adhesion between the plating layer and the material it was possible to produce a zinc-nickel alloy electro galvanized steel sheet having excellent chipping resistance improved about 30% or more chipping resistance.

상술한 바와 같이 본 발명에 따라 산세공정에서 염산농도를 증가시키지 않고도 염산용액에 산세촉진제를 첨가하여 도금소재 표면에 미소조도를 부여함으로써 염산의 농도를 증가시켰을 때의 경우 이상으로 칩핑 저항성 개선효과를 얻을 수 있으며, 산세촉진제를 사용하지 않았을 경우보다도 내칩핑성이 최소한 30% 이상 개선된 내칩핑성이 우수한 자동차용 아연-니켈 합금전기도금강판을 제조할 수 있게 되었다.As described above, the addition of an acid pickling accelerator to the hydrochloric acid solution without increasing the hydrochloric acid concentration in the pickling process gives a micro roughness to the surface of the plating material, thereby improving the chipping resistance. It is possible to obtain a zinc-nickel alloy electroplating steel sheet for automobiles having excellent chipping resistance improved at least 30% chipping resistance than when no pickling accelerator is used.

Claims (2)

연속전기도금라인의 산세공정에서 염산용액에 클루콘산 5 ~ 30%(wt.% 이하 같음), 과산화수소 5 ~ 40%, 인산나트륨 3 ~ 15%, 유기촉매제 5% 이하, 나머지는 물론 구성된 산세촉진제를 농도 12% 이하의 염산용액에 부피비율로 0.5%이상 ~ 10%이하 첨가한 것으로 에칭하므로써 강판표면에 미소조도가 형성되도록 한 것을 특징으로 하는 내칩핑성이 우수한 자동차용 아연-니켈 전기아연도금강판의 제조방법.In pickling process of continuous electroplating line, hydrochloric acid solution contains 5 to 30% of gluconic acid (same as wt.% Or less), hydrogen peroxide 5 to 40%, sodium phosphate 3 to 15%, organic catalyst of 5% or less, and the rest The zinc-nickel electro zinc plating for automobiles with excellent chipping resistance, characterized in that micro-roughness is formed on the surface of the steel sheet by etching by adding 0.5% or more to 10% or less in a hydrochloric acid solution having a concentration of 12% or less. Method of manufacturing steel sheet. 제 1 항에 있어서, 상기 미소조도를 가지는 에칭된 강판의 표면은 凹 면으로 형성되도록 한 것을 특징으로 하는 내칩핑성이 우수한 자동차용 아연 - 니켈 전기 아연도금강판의 제조방법.The method of claim 1, wherein the surface of the etched steel sheet having the micro roughness is formed to have a concave surface.
KR10-2001-0087645A 2001-12-28 2001-12-28 Manufacturing method of Zn-Ni electroplated steel sheet having a excellent chipping resistance by the addition of pickling accelerator KR100428025B1 (en)

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KR102126747B1 (en) 2019-10-30 2020-06-25 주식회사 켐프 Method for electro galvanizing of steel material with excellent adhesion, resistance brittle and corrosion resistance
KR102126746B1 (en) 2019-10-30 2020-06-25 주식회사 켐프 The electro-galvanizing method of the steel material for reducing wastewater and hydrogen embrittlement with using eco-friendly composition
KR102228885B1 (en) 2020-06-18 2021-03-18 주식회사 켐프 Surface treatment method for electro-galvanizing of steel materials and for coloring the electro-galvanized surface

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JPH02185987A (en) * 1989-01-12 1990-07-20 Kawasaki Steel Corp Production of zinc alloy electroplated steel sheet having superior adhesion of plating
JPH07331483A (en) * 1994-06-06 1995-12-19 Kobe Steel Ltd Production of electrogalvanized steel sheet
JP3557782B2 (en) * 1995-06-14 2004-08-25 株式会社神戸製鋼所 Manufacturing method of electrogalvanized steel sheet with excellent appearance
JP2000054187A (en) * 1998-07-31 2000-02-22 Sumitomo Metal Ind Ltd Production of galvanized metallic sheet
JP2003064493A (en) * 2001-08-24 2003-03-05 Sumitomo Metal Ind Ltd Electrogalvanized steel sheet having excellent appearance

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KR102126747B1 (en) 2019-10-30 2020-06-25 주식회사 켐프 Method for electro galvanizing of steel material with excellent adhesion, resistance brittle and corrosion resistance
KR102126746B1 (en) 2019-10-30 2020-06-25 주식회사 켐프 The electro-galvanizing method of the steel material for reducing wastewater and hydrogen embrittlement with using eco-friendly composition
KR102228885B1 (en) 2020-06-18 2021-03-18 주식회사 켐프 Surface treatment method for electro-galvanizing of steel materials and for coloring the electro-galvanized surface

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