KR19990053147A - Pickling liquid composition containing corrosion inhibitor additive and pickling method thereof - Google Patents

Pickling liquid composition containing corrosion inhibitor additive and pickling method thereof Download PDF

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KR19990053147A
KR19990053147A KR1019970072738A KR19970072738A KR19990053147A KR 19990053147 A KR19990053147 A KR 19990053147A KR 1019970072738 A KR1019970072738 A KR 1019970072738A KR 19970072738 A KR19970072738 A KR 19970072738A KR 19990053147 A KR19990053147 A KR 19990053147A
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pickling
acid
corrosion inhibitor
corrosion
inhibitor additive
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KR100348736B1 (en
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박노범
남태현
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이구택
포항종합제철 주식회사
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    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

본 발명은 금속의 산세공정에 있어서,무기산 혹은 유기산등의 산 수용액에 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 부식억제용 첨가제를 첨가함으로서 금속의 산세시의 소지부식을 억제하는 것을 특징으로 하는 금속의 산세방법에 관한 것으로서 특히 상기 부식억제용 첨가제로는 라우릴아민,4-에톡시-1,3-페닐렌디아민디하이드로클로라이드 및 이들의 혼합물을 적게는 1종 혹은 그 이상으로 하여 무기산 혹은 유기산등의 산 수용액에 첨가하는 것이 바람직하다. 또한 본 발명에 있어서는 상기 부식억제용 첨가제의 총배합량은 0.02-10g/L이며 나머지는 무기산 혹은 유기산등의 산 수용액 및 산세촉진제로 구성된 것을 특징으로 하는 산세액 조성물에 관한 것을 요지로 하고 있다.According to the present invention, in the pickling process of metal, the addition of corrosion inhibitor additives of laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride to an acid aqueous solution such as an inorganic acid or an organic acid, The present invention relates to a method for pickling metals, characterized by suppressing corrosion of the body. Especially, the corrosion inhibitor additive includes laurylamine, 4-ethoxy-1,3-phenylenediamine dihydrochloride and mixtures thereof. It is preferable to add 1 type or more to acid aqueous solution, such as an inorganic acid or an organic acid. In addition, in the present invention, the total compounding amount of the corrosion inhibitor additive is 0.02-10 g / L, and the rest of the present invention relates to an acid wash liquid composition comprising an acid solution such as an inorganic acid or an organic acid and an acid pickling accelerator.

Description

부식억제용 첨가제를 함유한 산세액 조성물 및 그 산세방법Pickling liquid composition containing corrosion inhibitor additive and pickling method thereof

본 발명은 금속의 산세공정에 있어서, 금속표면에 부착된 산화물 피막(녹 및 열연 밀 스케일)의 제거시 부식억제용 첨가제를 첨가한 산세액 조성물 및 상기 산세액 조성물에 의한 산세방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pickling liquid composition to which a corrosion inhibitor additive is added during removal of an oxide film (rust and hot rolling scale) attached to a metal surface in a metal pickling process and a pickling method using the pickling liquid composition.

일반적으로 열연강판과 같이 열처리를 실시한 금속재료의 표면에는 산화물피막이 부착되어 있으며 후공정인 냉연 및 도금공정등에 공급하기 위하여 이러한 산화물 피막을 제거할 필요가 있다. 이들 금속의 표면에 부착된 산화물 피막의 제거에는 황산, 염산, 인산, 초산, 설파민산등의 무기산 또는 유기산 및 이들의 혼산등의 수용액으로 산세를 행하고 있다. 또한 이들 산은 산세시에 산화물 피막이나 스케일을 용해하기도 하지만 금속소지도 동시에 용해하기 때문에 종래부터 소지부식의 방지를 위하여 부식억제제가 사용되어지고 있다. 그러나 모재보호를 위하여 사용하고 있는 부식억제제의 대부분은 산세속도를 느리게 하는 단점을 갖고 있다. 이 때문에 완전한 산세를 위하여는 더욱 긴 산세시간이 필요하며 모재의 부식 또한 진행하여 국부적인 과산세 현상이 발생하는등 품질 및 작업능률의 저하를 피할 수 없는 실정이다. 따라서 산세속도에 큰 영향을 주지 않고 모재의 부식을 억제시킬 수 있는 산세방법이 공업적으로 크게 요구되고 있다.In general, the oxide film is attached to the surface of the heat-treated metal material, such as hot rolled steel sheet, it is necessary to remove such oxide film in order to supply to the cold rolling and plating process, which is a post-process. To remove the oxide film adhered to the surface of these metals, pickling is carried out with an aqueous solution such as inorganic or organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sulfamic acid, and mixed acids thereof. In addition, these acids dissolve oxide films and scales at the time of pickling, but also dissolve metal bases at the same time. Therefore, corrosion inhibitors have been conventionally used to prevent corrosion of the body. However, most of the corrosion inhibitors used to protect the base metal have the disadvantage of slowing the pickling rate. For this reason, a longer pickling time is required for complete pickling, and the degradation of quality and work efficiency is inevitable, such as corrosion of the base material and local peracid pickling. Therefore, there is a great industrial demand for a pickling method that can suppress corrosion of the base material without significantly affecting the pickling speed.

종래에는 이러한 문제점을 해결하기 위하여 핵사메틸렌테트라아민을 염산수용액에 첨가하는 방법(일본국 특허공보 소 38-20708)등이 제안되었다. 그러나 상기 핵사메틸렌테트라아민을 염산수용액에 첨가하는 방법은 산세속도를 느리게 하여 미산세 방지를 위하여는 더욱 긴 산세시간이 소요될 뿐 아니라, 부분적인 소지부식 현상의 발생문제가 있는데, 특히 헤마타이트(Fe2O3)나 마그네타이트(Fe3O4)와 같은 난 산세성 스케일의 비율이 상대적으로 증가할수록 그 정도는 심해진다.Conventionally, in order to solve this problem, a method of adding nucleated methylenetetraamine to an aqueous hydrochloric acid solution (Japanese Patent Publication No. 38-20708) and the like have been proposed. However, the method of adding the nucleated methylenetetraamine to the aqueous solution of hydrochloric acid slows the pickling rate and takes longer pickling time to prevent the pickling, and there is a problem of the occurrence of partial branching corrosion, especially hematite (Fe). 2 O 3 ) and magnetite (Fe 3 O 4 ) as the ratio of the more difficult pickling scale increases, the degree becomes worse.

본 발명은 상기의 문제점을 해결하기 위하여 안출된 것으로서 종래 기술의 문제점인 소지금속의 국부적인 부식발생 문제를 현저히 억제시킬 수 있는 부식억제제용 첨가제를 함유한 산세액 조성물과 이 산세액 조성물에 의한 금속의 산세방법을 제공하는 것이 본 발명의 목적이다.The present invention has been made to solve the above problems, the pickling liquid composition containing a corrosion inhibitor additive capable of significantly suppressing the problem of local corrosion of the base metal which is a problem of the prior art and the metal by the pickling liquid composition It is an object of the present invention to provide a pickling method.

상기 목적을 달성하기 위하여 본 발명에서는 금속의 산세공정에 있어서,무기산 혹은 유기산등의 산 수용액에 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 부식억제용 첨가제를 첨가함으로서 금속의 산세시의 소지부식을 억제하는 금속의 산세방법을 제공하는 것을 특징으로 한다.In order to achieve the above object, in the present invention, in the pickling process of metal, an additive for inhibiting corrosion of laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride is added to an aqueous acid solution such as an inorganic acid or an organic acid. By providing a metal pickling method for suppressing the corrosion of the metal during pickling of the metal.

또한 본 발명에서는 상기 부식억제용 첨가제로 라우릴아민,4-에톡시-1,3-페닐렌디아민디하이드로클로라이드 및 이들의 혼합물을 적게는 1종 혹은 그 이상으로 하여 무기산 혹은 유기산등의 산 수용액에 첨가하여 금속의 산세시의 소지부식을 억제하는 금속의 산세방법을 제공하는 것을 특징으로 한다.In the present invention, as the corrosion inhibitor additive, laurylamine, 4-ethoxy-1,3-phenylenediamine dihydrochloride and mixtures thereof are at least one or more, and an aqueous solution of an acid such as an inorganic acid or an organic acid is used. It is characterized in that it provides a method for pickling metals to suppress the corrosion of the metals during pickling of metals.

또한 본 발명에서는 부식억제용 첨가제의 총배합량이 0.02-10g/L이 되고 나머지는 무기산 혹은 유기산등의 산 수용액 및 산세촉진제로 구성된 산세액 조성물을 제공하는 것을 특징으로 하고 있다.In addition, the present invention is characterized in that the total compounding amount of the corrosion inhibitor additive is 0.02-10g / L, the remainder is provided with a pickling liquid composition consisting of an acid aqueous solution, such as inorganic acids or organic acids and pickling accelerators.

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

본 발명은 금속의 산세공정에 있어서,라우릴아민[CH3(CH2)11NH2] 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드[C8H12N2O,2HCl]를 무기산 혹은 유기산등의 산 수용액에 첨가함으로서 소지의 국부적인 부식을 억제할 수 있도록 하는 부식억제용 첨가제를 제공하고 있다.In the acid pickling step of the metal, laurylamine [CH3 (CH2) 11NH2] and 4-ethoxy-1,3-phenylenediamine dihydrochloride [C8H12N2O, 2HCl] are added to an aqueous acid solution such as an inorganic acid or an organic acid. By providing an additive for inhibiting corrosion that can suppress local corrosion of the body.

본 발명에 사용된 부식억제용 첨가제 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 총 배합량은 0.02-10g/L이며 특히 0.5-10g/L가 바람직하다. 이들 부식억제용 첨가제인 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드는 1종 단독으로 혹은 2종이상 혼합해서 무기산 혹은 유기산등의 산수용액에 첨가하여 사용할 수 있으며 이때 산세촉진용 첨가제를 함께 첨가해도 무방하다. 상기 산세촉진용 첨가제는 예를들면, C2H3N3의 분자식을 갖는 트리아졸 화합물 과 C10HXN20(식중X는 10 혹은 12의 수소 수를 나타낸다.) 의 분자식을 갖는 페닐메틸피라졸 화합물을 예로들 수 있다.The total compounding amount of the corrosion inhibitor additive laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride used in the present invention is 0.02-10 g / L, particularly 0.5-10 g / L. These corrosion inhibitor additives, laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride, may be used alone or in combination of two or more thereof to acidic solutions such as inorganic or organic acids. Additives for acid pickling may be added together. The pickling accelerator additive is, for example, a triazole compound having a molecular formula of C 2 H 3 N 3 and a phenyl having a molecular formula of C 10 H X N 2 0 (wherein X represents a hydrogen number of 10 or 12). Methylpyrazole compounds are exemplified.

또한 본 발명에 사용한 부식억제용 첨가제 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 총 배합량을 0.02-10g/L의 농도로 한정한 이유는 0.02g/L 이하의 농도에서는 부식억제에 미치는 첨가제의 효과가 없고 10g/L 이상일 경우에는 효과가 포화하여 상한이상의 첨가는 용액의 안정성을 저하시키기 때문에 상기 부식억제용 첨가제는 그 함량을 0.1-10g/L로 제한하는 것이 바람직하다.In addition, the reason for limiting the total compounding amount of the corrosion inhibitor additive laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride used in the present invention to a concentration of 0.02-10 g / L is 0.02 g / L or less. At the concentration, there is no effect of the additive on corrosion inhibition, and when the concentration is more than 10 g / L, the effect is saturated and the addition of the upper limit lowers the stability of the solution. Therefore, the corrosion inhibitor additive is limited to 0.1-10 g / L. desirable.

이하 본 발명의 실시예에 대하여 구체적으로 설명한다.Hereinafter, embodiments of the present invention will be described in detail.

(실시예)(Example)

실시예 1-3 ; 1L 중에 염산 120g, 페닐메틸피라졸계 산세촉진제 1g 및 본 발명의 부식억제용 첨가제 2g을 함유한 80℃의 산세액에 저석 및 샌드페이퍼(#600)로 스케일 제거와 표면연마를 마친 열간압연강판(SPHC급, 직경 33mm, 두께 2.5mm)을 30분간 침적하여 강판의 무게변화를 관찰함으로서 첨가제의 부식억제능을 평가하였다. 그 결과는 표 1과 같다.Examples 1-3; Hot-rolled steel sheet (SPHC) finished with scale removal and surface polishing in a pickling solution at 80 ° C containing 120 g of hydrochloric acid, 1 g of phenylmethylpyrazole-based pickling accelerator, and 2 g of corrosion inhibitor additive according to the present invention. Grade, diameter 33mm, thickness 2.5mm) was immersed for 30 minutes to observe the weight change of the steel sheet to evaluate the corrosion inhibitory ability of the additive. The results are shown in Table 1.

비교예 1 ; 실시예 1-3 과 같은 조건에서 실험하였으며, 이 때 부식억제용 첨가제는 사용하지 않았다. 그 결과를 표 1에 나타내었다.Comparative Example 1; The experiment was carried out under the same conditions as in Example 1-3, in which no corrosion inhibitor additive was used. The results are shown in Table 1.

부식억제용 첨가제Corrosion Inhibitor Additives 강량무게(g)Intensity weight (g) 실시예 1Example 1 라우릴아민Laurylamine 0.26500.2650 실시예 2Example 2 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드4-ethoxy-1,3-phenylenediamine dihydrochloride 0.26580.2658 실시예 3Example 3 라우릴아민4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 혼합물A mixture of laurylamine 4-ethoxy-1,3-phenylenediamine dihydrochloride 0.26650.2665 비교예 1Comparative Example 1 무첨가No addition 0.39500.3950

실시예 4-6 ; 1L 중에 염산 120g, 페닐메틸피라졸계 산세촉진제 1g 및 본 발명의 부식억제용 첨가제 2g을 함유한 80℃의 산세액에 스케일이 부착된 열간압연강판(SPHC급)을 침적하여 표면의 스케일을 완전히 제거한 후 소지부식이 발생한 정도를 평가하였다. 소직부식의 발생정도는 육안관찰 및 주사전자현미경(SEM) 관찰을 통하여 1등급, 소지부식이 거의 없는 상태, 2등급; 소지부식 국부적 혹은 약간 발생, 3등급; 소지부식 발생으로 나누어 구분하였다. 그 결과는 표 2와 같다.Example 4-6; A hot rolled steel sheet (SPHC grade) with scales was deposited on a pickling solution at 80 ° C containing 120 g of hydrochloric acid, 1 g of phenylmethylpyrazole-based pickling accelerator, and 2 g of the corrosion inhibitor additive of the present invention in 1 L to completely remove scale from the surface. After the evaluation, the degree of body corrosion was evaluated. The incidence of small corrosive corrosion was grade 1, almost no body corrosion, grade 2 through visual observation and scanning electron microscopy (SEM) observation; Local or minor attack, grade 3; It was divided into the occurrence of body corrosion. The results are shown in Table 2.

비교예 2 ; 실시예 4-6과 같은 조건에서 실험하였으며, 이때 부식억제용 첨가제로 기존 핵사메틸렌타트라아민 2g이 사용되었다. 그 결과를 표 2에 나타내었다.Comparative Example 2; Experiments were carried out under the same conditions as in Example 4-6, wherein 2 g of nucleated methylenetatraamine was used as an additive for inhibiting corrosion. The results are shown in Table 2.

비교예3 ; 실시예 4-6과 같은 조건에서 실험하였으며, 이때 부식억제용 첨가제는 사용하지 않았다. 그 결과를 표 2에 나타내었다.Comparative Example 3; The experiment was conducted under the same conditions as in Example 4-6, wherein no corrosion inhibitor additive was used. The results are shown in Table 2.

부식억제용 첨가제Corrosion Inhibitor Additives 평가결과Evaluation results 실시예 4Example 4 라우릴아민Laurylamine 1등급Grade 1 실시예 5Example 5 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드4-ethoxy-1,3-phenylenediamine dihydrochloride 1등급Grade 1 실시예 6Example 6 라우릴아민4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 혼합물A mixture of laurylamine 4-ethoxy-1,3-phenylenediamine dihydrochloride 1등급Grade 1 비교예 2Comparative Example 2 핵사메틸렌테트라아민Nucleated methylenetetraamine 2등급Grade 2 비교예 3Comparative Example 3 무첨가No addition 3등급Grade 3

실시예 7-8 ; 1L중에 염산 120g, 페닐메틸피라졸계 산세촉진제 1g 및 본 발명의 부식억제용 첨가제를 각각 0.005-30g의 범위로 함유한 80℃의 산세액에 실시예 1-3의 조건과 동일한 조건의 열간압연강판을 30분 동안 침적하여 강판의 무게변화를 관찰함으로서 첨가제의 부식억제능을 평가하였다. 그 결과는 표 3과 같다.Example 7-8; Hot rolled steel sheet under the same conditions as in Example 1-3 in an acid pickling solution containing 120 g of hydrochloric acid, 1 g of phenylmethylpyrazole-based pickling accelerator, and the corrosion inhibitor additive of the present invention in the range of 0.005-30 g in 1 L. The corrosion inhibition ability of the additive was evaluated by immersing for 30 minutes to observe the weight change of the steel sheet. The results are shown in Table 3.

부식억제용 첨가제Corrosion Inhibitor Additives 첨가량(g/L)Addition amount (g / L) 감량무게(g)Weight loss (g) 실시예 7Example 7 라우릴아민Laurylamine 201020.50.020.005201020.50.020.005 0.26460.26460.26500.26710.32530.39490.26460.26460.26500.26710.32530.3949 실시예 8Example 8 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드4-ethoxy-1,3-phenylenediamine dihydrochloride 201050.50.020.005201050.50.020.005 0.26540.26540.26580.26780.32750.39500.26540.26540.26580.26780.32750.3950

표 1과 표 2의 실시예 1-6과 비교예 1-3으로부터 알 수 있듯이 산세액으로 120g/L의 염산을 사용한 80℃의 산세조건에서 본 발명의 산세억제용 첨가제 2g/L는 강판의 부식을 억제하는 데에 현저한 효과를 나타내었다. 특히 실시예3 alc 실시예 6과 같은 산세촉진용 첨가제 2종을 혼합한 경우는 단독으로 첨가한 실시예 1-2 및 실시예 4-5의 경우보다 산세강판의 표면이 밝아졌다. 또한 실시예 5 및 실시예 6은 실시예 4 보다 산세소요시간이 단축되었는데 이는 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드 화합물 속의 디하이드로클로라이드 성분의 존재에 기인한 것으로 추측된다. 또한 표 3의 실시예 7-8에 나타난 바와 같이 본 발명의 산세억제용 첨가제의 적정 첨가량은 0.02-10 g/L이고 특히 0.5-10g/L가 양호하며, 20g/L이상을 첨가할 경우는 용액이 불안정한 상태를 보였다.As can be seen from Examples 1-6 and Comparative Examples 1-3 of Table 1 and Table 2, the pickling inhibitor additive 2 g / L of the present invention was subjected to pickling at 80 ° C. using 120 g / L hydrochloric acid as the pickling solution. Significant effects have been shown in inhibiting corrosion. Example 3 alc In the case where two kinds of additives for pickling promotion as in Example 6 were mixed, the surface of the pickling steel sheet became brighter than in the case of Examples 1-2 and Examples 4-5 added alone. In addition, the pickling time of Example 5 and Example 6 was shorter than that of Example 4, which is presumably due to the presence of the dihydrochloride component in the 4-ethoxy-1,3-phenylenediamine dihydrochloride compound. In addition, as shown in Example 7-8 of Table 3, the proper amount of the pickling inhibitor additive of the present invention is 0.02-10 g / L, in particular, 0.5-10 g / L is good, and when more than 20 g / L is added, The solution showed an unstable state.

Claims (4)

금속의 산세공정에 있어서,무기산 혹은 유기산등의 산 수용액에 라우릴아민 및 4-에톡시-1,3-페닐렌디아민디하이드로클로라이드의 부식억제용 첨가제를 첨가함으로서 금속의 산세시의 소지부식을 억제하는 것을 특징으로 하는 금속의 산세방법.In the pickling process of metals, the corrosion of the metal during pickling is added by adding a corrosion inhibitor additive of laurylamine and 4-ethoxy-1,3-phenylenediamine dihydrochloride to an acid aqueous solution such as an inorganic acid or an organic acid. A method for pickling metals, which is suppressed. 제1항에 있어서, 상기 부식억제용 첨가제로는 라우릴아민,4-에톡시-1,3-페닐렌디아민디하이드로클로라이드 및 이들의 혼합물을 적게는 1종 혹은 그 이상으로 하여 무기산 혹은 유기산등의 산 수용액에 첨가하여 금속의 산세시의 소지부식을 억제하는 것을 특징으로 하는 금속의 산세방법.According to claim 1, Corrosion inhibitor additives, such as laurylamine, 4-ethoxy-1,3-phenylenediamine dihydrochloride and mixtures thereof at least one or more of the inorganic acid or organic acid, etc. A method of pickling metals, characterized in that it is added to an aqueous acid solution to suppress the corrosion of the body during pickling of the metal. 제2항에 있어서, 상기 산 수용액에 산세촉진제를 더욱 첨가하는 것을 특징으로 하는 금속의 산세방법.The method of pickling metals according to claim 2, wherein an acid pickling accelerator is further added to the acid aqueous solution. 제1항 또는 제2항에 있어서, 상기 부식억제용 첨가제의 총배합량은 0.02-10g/L이며 나머지는 무기산 혹은 유기산등의 산 수용액 및 산세촉진제로 구성된 것을 특징으로 하는 산세액 조성물.The pickling liquid composition according to claim 1 or 2, wherein the total amount of the corrosion inhibitor additive is 0.02-10 g / L, and the remainder is composed of an aqueous acid solution such as an inorganic acid or an organic acid and an acid pickling accelerator.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100967713B1 (en) * 2008-03-31 2010-07-07 주식회사 포스코 Method for treating a surface of a magnesium alloy and magnesium alloy provided with a treated surface
KR20200081087A (en) 2018-12-27 2020-07-07 남동화학(주) Picking solution for hot dip galvanizing process and method of manufacturing the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100967713B1 (en) * 2008-03-31 2010-07-07 주식회사 포스코 Method for treating a surface of a magnesium alloy and magnesium alloy provided with a treated surface
KR20200081087A (en) 2018-12-27 2020-07-07 남동화학(주) Picking solution for hot dip galvanizing process and method of manufacturing the same

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