KR950014077B1 - Surface etching solution of galvanized steel sheets and etching method for using the same - Google Patents
Surface etching solution of galvanized steel sheets and etching method for using the same Download PDFInfo
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- KR950014077B1 KR950014077B1 KR1019930015398A KR930015398A KR950014077B1 KR 950014077 B1 KR950014077 B1 KR 950014077B1 KR 1019930015398 A KR1019930015398 A KR 1019930015398A KR 930015398 A KR930015398 A KR 930015398A KR 950014077 B1 KR950014077 B1 KR 950014077B1
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- 238000005530 etching Methods 0.000 title claims abstract description 63
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 30
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000007711 solidification Methods 0.000 claims abstract description 5
- 230000008023 solidification Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 10
- 239000010959 steel Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 2
- 229910020148 K2ZrF6 Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910020218 Pb—Zn Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
- C23C2/52—Controlling or regulating the coating processes with means for measuring or sensing
- C23C2/526—Controlling or regulating the coating processes with means for measuring or sensing for visually inspecting the surface quality of the substrate
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Quality & Reliability (AREA)
- Coating With Molten Metal (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
제 1 도는 에칭 전 및 본 발명에 따라 에칭한 후의 용융아연도금강판 표면에 대한 표면 관찰 사진.1 is a photograph of the surface observation of the surface of a hot-dip galvanized steel sheet before etching and after etching according to the present invention.
제 2 도는 에칭 전 및 본 발명에 따라 에칭한 후의 용융아연도금강판 표면에 대한 주사전자현미경 관찰사진.2 is a scanning electron microscope photograph of the surface of a hot dip galvanized steel sheet before etching and after etching according to the present invention.
본 발명은 용융아연도금강판의 표면에칭용액 및 이 용액을 사용하여 용융아연도금강판의 표면을 에칭하는 방법에 관한 것이다.The present invention relates to a surface etching solution of a hot dip galvanized steel sheet and a method for etching the surface of a hot dip galvanized steel sheet using the solution.
아연도금강판은 강판에 대한 뛰어난 희생 방식 효과와 저렴한 가격으로 현재 철강산업에 있어서 표면처리 강판의 주류를 점하고 있다.Galvanized steel sheets dominate the surface-treated steel sheets in the steel industry at this time due to their excellent sacrificial effects and low price.
특히, 아연도금강판의 제조방법중 강판을 용융된 아연에 침적시켜 표면처리하는 용융아연도금강판은 아연도금의 부착량을 두텁게 할 수 있고 광택성이 우수한 외관을 얻을 수 있다는 점에서 다른 방법보다 널리 채용되고 있다.In particular, the hot-dip galvanized steel sheet in which the steel sheet is deposited on molten zinc and surface-treated in the manufacturing method of the galvanized steel sheet is widely adopted than other methods in that it can thicken the amount of zinc plating and obtain an excellent gloss appearance. It is becoming.
이 용융아연도금강판 제조시에는 용융되었던 아연이 응고하면서 스팽글(Spagle)이라는 광택을 갖는 독특한 형상의 응고조직을 형성하게 된다.In the production of the hot-dip galvanized steel sheet, the molten zinc solidifies to form a solidified structure having a unique shape having a gloss called a sparkle.
이 스팽글은 도금 조건에 따라 그 크기가 변환하며 이에 의하여 강판전체의 광택등의 외관도 크게 영향을 받게 된다.The size of the sequins is changed depending on the plating conditions, and the appearance of the gloss and the like of the whole steel sheet is also greatly affected.
따라서, 강판표면에 형성되는 스팽글의 크기 및 형상을 측정하는 것이 중요하나 특유의 광택으로 사진촬영등을 통한 측정이 곤란하다.Therefore, it is important to measure the size and shape of the sequins formed on the surface of the steel sheet, but it is difficult to measure through photography, etc. due to the unique gloss.
또한, 스팽글은 용융아연이 응고하면서 결정되는 결정의 성장 방향에 의해 여러가지 종류로 나뉘어지지만 도금층의 표층에는 용융아연도금욕에 첨가되는 Al의 산화물이 형성되므로 아연도금의 결정을 육안이나 주사전자현미경으로 직접 관찰하는 것이 곤란하다.In addition, sequins are divided into various types according to the growth direction of crystals determined by solidification of molten zinc. However, zinc oxide is added to the surface layer of the plating layer by forming an oxide of Al added to the hot dip galvanizing bath. It is difficult to observe directly.
종래에는 아연도금강판상에 형성되는 스팽글의 크기를 결정하기 위하여 용융아연도금강판에 투명한 종이등을 이용하여 직접 그려서 측정하거나 에칭액을 이용하여 부식시킨 후 화상분석기등을 이용하여 그 크기를 측정하였다.Conventionally, in order to determine the size of the sequins formed on the galvanized steel sheet, the hot dip galvanized steel sheet was directly drawn using a transparent paper or the like, or corroded using an etching solution, and then the size thereof was measured using an image analyzer.
후자에서와 같이 부식시킨 후 스팽글 크기등을 측정하기 위하여 사용되는 에칭용액 및 이 용액을 이용하여 에칭하는 방법으로는 다음과 같이 방법들이 공지되어 있으며, 그 대표적인 방법으로는 CrO3: 200g, H2O : 950cc, ZnSO4ㆍ7H2O : 4g 및 질산 5cc로 이루어진 1차 용액에 2-5분 동안 시편을 침적한 후, 다시 CrO3200g/l의 2차용액에 10-30초동안 침적한 후에 수세를 한 다음, H2O : 100cc, 염산 : 7-8cc, 및 과산화수소 : 10cc로 조성되는 3차 용액에 5-10초간 침적처리를 행한 후 다시 시편을 진한 염산의 4차 용액에 1-2초동안 침적한 후, 수세를 행하여 용융아연도금강판을 에칭하는 방법을 들 수 있다.(일본 금속표면기술 24권 1호 13페이지) 또다른 방법으로는 용융아연도금강판의 표면을 연마한 후 CrO3200g/l, NaSO4: 15g/l로 조성되는 용액에 10-20초동안 침적시켜 에칭하는 방법을 들 수 있다(Metallurgical Transaction 13, 1978년 581페이지). 그러나, 상기한 종래 방법중 전자의 경우에는 에칭에 소요되는 용액량이 많고 사용되는 용액의 종류도 많으며, 여러공정을 거쳐야 하므로 만족할만한 결과를 얻기 위해서는 세심한 주의와 숙련된 기술이 요구되며 후자의 경우에는 전자보다는 간편하지만, 아연도금강판의 표면을 연마해야만 하는 문제점이 있다.The etching solution used to measure the sequin size and the like after the corrosion as in the latter and the method of etching using this solution is known as follows, the representative method is CrO 3 : 200g, H 2 O: 950cc, ZnSO 4 ㆍ 7H 2 O: 4g and 5cc nitric acid in the primary solution was deposited for 2-5 minutes, and then again in a secondary solution of CrO 3 200g / l for 10-30 seconds. After washing with water, the solution was immersed in a tertiary solution composed of H 2 O: 100cc, hydrochloric acid: 7-8cc, and hydrogen peroxide: 10cc for 5-10 seconds, and then the specimen was again subjected to 1-d. After immersion for 2 seconds, washing with water is performed to etch the hot-dip galvanized steel sheet (Japanese Metal Surface Technology No. 24, No. 1 page 13). Another method is to polish the surface of the hot-dip galvanized steel sheet. 200 g / l CrO 3 , NaSO 4 : Etched by dipping for 10-20 seconds in a solution composed of 15 g / l A method (Metallurgical Transaction 13, p. 581, 1978). However, in the former method, the former requires a large amount of solution for etching and a large number of types of solutions to be used, and requires many steps, so that careful attention and skill are required to obtain satisfactory results. Although simpler than the former, there is a problem in that the surface of the galvanized steel sheet must be polished.
또한, 상기 종래 방법들은 공통적으로 독성이 강한 CrO3를 다량 함유하고 있으므로 취급시 상당히 안전에 유의하여야 하며 에칭이 끝난 후에는 다량의 중금속을 함유한 폐수가 발생하게 되는 문제점도 있다.In addition, since the conventional methods generally contain a large amount of highly toxic CrO 3 , it should be considerably safe in handling, and there is also a problem in that wastewater containing a large amount of heavy metal is generated after etching.
또한, 상기 종래 방법으로는 용융아연도금의 응고 조직을 관찰하는 것은 불가능하므로, 현재 응고조직의 관찰은 X-선 회절시험을 통하여 간접적으로 관찰하고 있는 실정이다.In addition, it is impossible to observe the coagulated structure of the hot dip galvanized by the conventional method, the current situation is observed indirectly through the X-ray diffraction test.
이에, 본 발명자는 상기하 종래 방법들의 문제점을 해결하기 위하여 본 발명을 제안하게 된 것으로서, 본 발명은 용융아연도금강판의 표면을 에칭할시 사용하기 간편하고 안전한 에칭 용액 및 이 에칭용액을 이용하여 강판 표면의 스팽글의 크기와 조직을 용이하고 신속하게 측정할 수 있는 에칭방법을 제공하고자 하는데, 그 목적이 있다.Accordingly, the present inventors have proposed the present invention to solve the problems of the conventional methods described above, and the present invention uses a simple and safe etching solution and this etching solution when etching the surface of the hot-dip galvanized steel sheet An object of the present invention is to provide an etching method capable of easily and quickly measuring the size and structure of sequins on a steel sheet surface.
이하, 본 발명에 대하여 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated.
본 발명은 H2O 1000ml에 5-10g/l의 CrO3및 0.5-1.0g/l의 K2ZrF6를 첨가하여 조성되는 용융아연도금 강판의 표면에칭 용액에 관한 것이다.The present invention relates to a surface etching solution of a hot dip galvanized steel sheet prepared by adding 5-10 g / l CrO 3 and 0.5-1.0 g / l K 2 ZrF 6 to 1000 ml of H 2 O.
또한, 본 발명은 표면에 형성되는 스팽글의 크기와 응고조직을 관찰하기 위하여 용융아연도금 강판 표면을 에칭하는 방법에 있어서, H2O 1000ml에 5-10g/l의 CrO3및 0.5-1.0g/l의 K2ZrF6를 첨가하여 조성되는 에칭용액을 50-60℃로 유지시킨 후, 이 용액에 용융아연도금강판을 침적시켜 25-35분동안 에칭시킨 다음, 수세 및 건조하여 용융아연도금강판 표면을 에칭하는 방법에 관한 것이다.In addition, the present invention is a method of etching the surface of the hot-dip galvanized steel sheet to observe the size and solidification structure of the sequins formed on the surface, 5-10g / l of CrO 3 and 0.5-1.0g / in 1000ml of H 2 O After maintaining the etching solution formed by adding l K 2 ZrF 6 at 50-60 ° C, the hot dip galvanized steel plate was immersed in this solution for etching for 25-35 minutes, washed with water and dried to hot-dip galvanized steel sheet. A method of etching a surface.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
상기 CrO3는 용융아연도금강판의 표면을 산화, 용출시키는 작용을 하는 것으로서, 그 첨가량이 5g/l이하인 경우에는 에칭의 효과가 크지 않고, 10g/l이상인 경우에는 Cr이 표면의 아연과 반응하여 크롬피막을 형성하므로 착색이 발생하는 단점이 있으므로, 상기 CrO3의 첨가량은 5-10g/l로 제한하는 것이 바람직하다.The CrO 3 acts to oxidize and elute the surface of the hot-dip galvanized steel sheet. When the added amount is 5 g / l or less, the effect of etching is not large, and when 10 g / l or more, Cr reacts with zinc on the surface. Since the formation of the chromium coating has a disadvantage in that coloring occurs, the amount of CrO 3 added is preferably limited to 5-10 g / l.
본 발명에 소요되는 CrO3의 양은 종래 방법에 비하여 2.5-5.0%에 불과하므로 중금속 폐수의 발생이 상대적으로 적은 장점을 갖게 된다.Since the amount of CrO 3 required in the present invention is only 2.5-5.0% compared to the conventional method, the generation of heavy metal waste water has a relatively low advantage.
상기 K2ErF6는 성분중의 불소가 아연의 균일한 에칭을 도와주고 원소중의 Zr은 표면에 석출하게 되는데, 표면의 결정방향에 따라 석출의 차이가 발생하여 에칭된 표면의 명암차이를 두드러지게 하는 역할을 하는 성분으로써, 그 첨가량이 0.5g/l이하인 경우에는 첨가효과가 미약하고, 1.0g/l이상인 경우에는 균일한 에칭이 곤란할 뿐만 아니라 부분적으로 과부식이 되기 때문에 상기 K2ZrF6의 첨가량은 0.5-10g/l로 제한하는 것이 바람직하다.The K 2 ErF 6 is a fluorine in the component to help the uniform etching of zinc and Zr in the element precipitates on the surface, the difference in precipitation occurs according to the crystal direction of the surface, the difference in contrast of the etched surface is remarkable As a component that acts as a preservative, when the addition amount is 0.5g / l or less, the effect of addition is weak, and when it is 1.0g / l or more, not only uniform etching is difficult but also partially overcorrosion, so that K 2 ZrF 6 The amount of addition is preferably limited to 0.5-10 g / l.
본 발명의 에칭방법에 있어, 에칭용액의 온도는 50-60℃로 제한하는 것이 바람직한데, 그 이유는 50℃이하인 경우에는 에칭작용이 충분하지 못하여 시간이 오래 걸리고, 60℃이상인 경우에는 유독한 증기가 발생할 뿐만 아니라 과부식이 되기 때문이다.In the etching method of the present invention, it is preferable to limit the temperature of the etching solution to 50-60 ° C., since the etching action is not sufficient when the temperature is 50 ° C. or less, and it is long when it is 60 ° C. or more. Not only does it generate steam, but it is also overcorroded.
한편, 본 발명에 적용될 수 있는 용융아연도금강판은 연마등의 전처리가 필요없고, 또한, 크로메이트 처리된 강판도 본 발명에 적용될 수 있다.On the other hand, the hot-dip galvanized steel sheet that can be applied to the present invention does not require pretreatment such as polishing, and the chromate-treated steel sheet can also be applied to the present invention.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예 1]Example 1
0.12% Al-0.08% Pb-Zn으로 조성되는 용융도금욕을 사용하여 용융아연도금된 용융아연도금강판을 하기 표 1과 같이 조성되는 에칭용액을 사용하여 하기 표 1과 같은 에칭조건으로 에칭한 다음, 강판표면의 에칭정도를 육안으로 관찰하고, 그 관찰결과를 하기표 1에 나타내었다.The hot dip galvanized steel sheet hot-dip galvanized using a hot dip bath composed of 0.12% Al-0.08% Pb-Zn was etched under the etching conditions shown in Table 1 below using an etching solution composed as shown in Table 1 below. , The degree of etching of the surface of the steel sheet was visually observed, and the results are shown in Table 1 below.
[표 1]TABLE 1
○ : 우수(조직에칭이 잘됨)○: Excellent (excellent organization etching)
△ : 에칭 약함(조직관찰 곤란)Δ: weak etching (difficult to observe tissue)
× : 에칭 심함(관찰 불가능)×: Etching severe (non-observation)
상기 표 1에 나타난 바와같이, 본 발명에 따라 에칭시킨 발명에(a-i)의 경우에는 우수한 에칭 표면이 얻어짐을 알 수 있다.As shown in Table 1, in the case of the invention (a-i) etched according to the present invention, it can be seen that an excellent etching surface is obtained.
그러나, 크롬산의 첨가량이 본 발명의 하한값보다 적은 비교예(1,2)는 에칭 정도가 미약하고, 크롬산의 첨가량이 본 발명의 상한값보다 많은 비교예(9,10,11)의 경우에는 에칭이 심하게 되어 조직관찰이 어려움을 알 수 있다.However, the comparative examples (1, 2) in which the amount of chromic acid added is lower than the lower limit of the present invention have a weak etching degree, and in the case of the comparative examples (9, 10, 11) in which the amount of chromic acid added is higher than the upper limit of the present invention, the etching is not performed. It can be hard to observe organizational difficulties.
또한, K2ZrF6의 첨가량이 본 발명의 하한값보다 적은 비교예(3)의 경우에는 에칭정도가 미약하고 본 발명의 상한값보다 많은 비교예(8)의 경우에는 에칭이 심하게 되어 조직관찰이 어려움을 알 수 있다.In addition, in the case of Comparative Example (3) in which the amount of K 2 ZrF 6 added was less than the lower limit of the present invention, the degree of etching was weak, and in the case of Comparative Example (8) in which the amount of K 2 ZrF 6 was more than the upper limit of the present invention, the etching was severe and difficult to observe the tissue. It can be seen.
또한, 강판의 에칭시 에칭용액의 온도 및 에칭 시간이 본 발명의 범위를 벗어나는 비교예(4,5) 및 (6,7)의 경우에는 적절한 에칭이 불가능함을 알수 있다.In addition, it can be seen that in the case of Comparative Examples (4,5) and (6,7) in which the temperature and etching time of the etching solution during the etching of the steel sheet are outside the scope of the present invention, proper etching is impossible.
[실시예 2]Example 2
상기 실시예 1에서와 같이 준비된 용융아연도금강판의 표면에 대하여 에칭전과 본 발명에 따라 에칭한 후의 표면 관찰 사진과 주자전자현미경(×1000배)관찰사진을 조사하고, 그 결과를 제 1 도a에는 에칭전의 표면관찰사진을, 제 1 도b에는 에칭후의 표면 관찰사진을 나타내고, 제 2 도a에는 에칭전의 주사전자 현미경 관찰사진을, 제 2 도b에는 에칭후의 주사전자현미경 관찰사진을 나타내었다.On the surface of the hot-dip galvanized steel sheet prepared as in Example 1 above, the surface observation photograph and the electron electron microscope (× 1000 times) observation photograph before etching and after etching according to the present invention were examined, and the results are shown in FIG. The surface observation photograph before etching is shown in FIG. 1, the surface observation photograph after etching is shown in FIG. 1B, the scanning electron microscope photograph before etching is shown in FIG. 2A, and the scanning electron microscope photograph after etching is shown in FIG. .
제 1 도에 나타난 바와같이, 본 발명에 따라 에칭한 경우에는 뚜렷한 명암차를 얻을 수 있어 스팽글의 크기 측정이 용이함을 알 수 있다.As shown in FIG. 1, in the case of etching according to the present invention, a clear contrast difference can be obtained, and it can be seen that the size of the sequins is easily measured.
또한, 제 2 도에 나타난 바와같이, 에칭처리전에는 표면에 Al등의 산화막이 형성되어 아연의 응고조직 관찰이 곤란한 반면에, 본 발명에 따라 에칭하는 경우에는 아연특유의 육방정계 구조의 육각형을 보이며 성장해 있는바, 이로부터 본 발명에 따라 에칭하는 경우에는 응고조직의 관찰도 가능하게 됨을 알 수 있다.In addition, as shown in FIG. 2, before the etching process, an oxide film such as Al is formed on the surface, making it difficult to observe the coagulation structure of zinc. On the other hand, when etching according to the present invention, the hexagonal hexagonal structure peculiar to zinc is shown. As a result, it can be seen that when the etching is carried out according to the present invention, the solidified structure can be observed.
상술한 바와같이, 본 발명은 신규한 에칭용액을 사용하여 전처리하지 않은 용융아연도금강판이라도 효과적으로 에칭할 수 있고 응고조직까지 관찰이 가능하므로 용융아연도금강판의 제조시 스팽글 크기의 관리등에 효율적으로 사용할 수 있으며, 용융아연의 응고조직에 대한 효과적인 연구를 가능하게 하는 효과가 있는 것이다.As described above, the present invention can effectively etch even hot-dip galvanized steel sheet that has not been pretreated by using a novel etching solution, and can observe the solidification structure. Therefore, the present invention can be efficiently used for the management of sequin size when manufacturing hot-dip galvanized steel sheet. It may be effective to enable an effective study on the coagulation structure of molten zinc.
Claims (2)
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| US8535552B2 (en) | 2009-07-27 | 2013-09-17 | Hyundai Steel Company | Method of evaluating center segregation of continuous cast slab |
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| US8535552B2 (en) | 2009-07-27 | 2013-09-17 | Hyundai Steel Company | Method of evaluating center segregation of continuous cast slab |
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