KR0124828B1 - Manufacturing method for zinc dipped steel sheet with zero-spangle - Google Patents
Manufacturing method for zinc dipped steel sheet with zero-spangleInfo
- Publication number
- KR0124828B1 KR0124828B1 KR1019940026953A KR19940026953A KR0124828B1 KR 0124828 B1 KR0124828 B1 KR 0124828B1 KR 1019940026953 A KR1019940026953 A KR 1019940026953A KR 19940026953 A KR19940026953 A KR 19940026953A KR 0124828 B1 KR0124828 B1 KR 0124828B1
- Authority
- KR
- South Korea
- Prior art keywords
- steel sheet
- hot
- galvanized steel
- dip galvanized
- spangle
- Prior art date
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 30
- 239000010959 steel Substances 0.000 title claims abstract description 30
- 239000011701 zinc Substances 0.000 title claims abstract description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910001335 Galvanized steel Inorganic materials 0.000 claims abstract description 41
- 239000008397 galvanized steel Substances 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005507 spraying Methods 0.000 claims abstract description 14
- 238000005246 galvanizing Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 241000519995 Stachys sylvatica Species 0.000 description 5
- 229910017053 inorganic salt Inorganic materials 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- NIXNJPJBNVFXEG-UHFFFAOYSA-N [K].[K].[Cr] Chemical compound [K].[K].[Cr] NIXNJPJBNVFXEG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- PYKNDCILXQWMJP-UHFFFAOYSA-N azane;chromium(3+) Chemical compound N.[Cr+3] PYKNDCILXQWMJP-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003746 surface roughness Effects 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
- 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
- C23C2/26—After-treatment
- C23C2/265—After-treatment by applying solid particles to the molten coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
- B05C11/06—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface with a blast of gas or vapour
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/007—After-treatment
-
- 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
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
Description
본 발명은 자동차용, 가전용 및 건자재용으로 사용되는 고광택 제로스팡글 용융아연 도금강판의 제조방법에 관한 것으로, 보다 상세히 도금욕에 Sb를 첨가하여 용융아연 도금한 후, 인산염계 수용액을 분사하므로서 용융아연 도금강판의 표면에 스팡글이 존재하지 않으며 광택성이 극히 우수한 제로스팡글 용융아연 도금강판 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a high-gloss zerospangle hot-dip galvanized steel sheet used for automobiles, home appliances and building materials, and in more detail by adding Sb to the plating bath and then hot-dip zinc plating, melting by spraying a phosphate-based aqueous solution The present invention relates to a method for manufacturing a zerospangle hot dip galvanized steel sheet having no spangles on the surface of the galvanized steel sheet and having excellent luster.
일반적으로 용융아연 도금강판은 전기아연 도금강판에 비하여 외관이 미려하지 못할 뿐만 아니라 도금된 강판 표면이 평활하지 못하여 그 용도에 있어서 제한을 받아 왔다.In general, hot-dip galvanized steel sheet has been limited in its use because the appearance of the hot-dip galvanized steel sheet is not only beautiful but also the surface of the plated steel sheet is not smooth.
그러나 상기와 같은 용융 아연도금강판은 제조비용이 쌀 뿐만 아니라 많은 양이 아연을 도금할 수 있어 내식성이 우수한 장점을 가지고 있으므로, 이러한 장점을 이용하기 위하여 용융아연 도금강판의 도금표면 품질을 개선하려는 노력이 증대되었고, 그 결과 최근에는 새로운 기술이 개발되어 용융아연 도금강판의 외관 품질이 전기아연 도금강판의 외관품질과 대등하게 되어 그 수요가 날로 증가하고 있는 추세이다.However, the hot-dip galvanized steel sheet as described above has the advantage of excellent corrosion resistance because it is not only cheap production cost but also a large amount of zinc can be plated, efforts to improve the plating surface quality of the hot-dip galvanized steel sheet in order to take advantage of these advantages As a result, in recent years, a new technology has been developed and the appearance quality of hot-dip galvanized steel sheet is equal to the appearance quality of galvanized steel sheet, and the demand is increasing day by day.
통상적으로 강판의 용융아연 도금시 도금욕의 성분은 A1 : 0.10-0.20wt%, Pb : 0.05-0.20 wt%(또는 Sb ; 0.05-0.20wt%), 불가피한 불순원소인 Cd, Sn 등의 합계 ; 0.02wt% 이하, Fe : 0.01-0.05wt%, 잔부 Zn로 조성되며, 상기와 같은 조성을 갖는 도금욕에서 용융아연 도금을 하면 도금된 강판 표면에 아연의 응고결정인 스팡글이 꽃모양으로 성장하여 형성된다.In general, the components of the plating bath in hot dip galvanizing of steel sheets include A1: 0.10-0.20 wt%, Pb: 0.05-0.20 wt% (or Sb; 0.05-0.20 wt%), and inevitable impurities such as Cd and Sn; It is composed of 0.02wt% or less, Fe: 0.01-0.05wt%, balance Zn, and when hot-dip galvanizing is performed in the plating bath having the composition as described above, the spangle, which is a solidification crystal of zinc, grows on the surface of the plated steel sheet. Is formed.
상기와 같이 도금된 강판표면에 꽃모양의 스팡글을 갖는 용융아연도금 제품을 레귤러 스팡글(regular-spangle)이라 하며, 이러한 스팡글이 강판 표면상에 형성되면 표면 조도가 증가하여 강판 표면이 평활하지 못하며, 도장시 도료와의 밀착성이 불량하고, 또한 도장후에도 스팡글에 의한 도금강판의 표면 요철이 제거되지 않을 뿐만 아니라 스팡글이 도장피복층을 투과하여 나타나므로서 선영성을 해치게 되어 용융아연 도금강판의 외관이 불량하게 되는 문제점이 있다.The hot-dip galvanized product having flower-shaped spangles on the plated steel plate surface is called regular spangle. When such spangles are formed on the steel plate surface, the surface roughness increases and the steel plate surface is smoothed. When coating, the adhesion with paint is poor, and even after coating, the surface irregularities of the plated steel plate are not removed by the spangles, and the spangles penetrate through the coating coating layer, thereby spoiling the sensibility. There is a problem that the appearance of the steel sheet is poor.
따라서 도금강판 표면에 스팡글이 없는 제로스팡글 용융아연 도금강판을 제조하기 위한 여러방법이 제안되어 사용되고 있다.Therefore, various methods have been proposed and used for producing a zerospangle hot dip galvanized steel sheet having no spangles on the surface of the coated steel sheet.
상기와 같이 용융아연 도금된 강판 표면에 스팡글이 없는 제로스팡글 제품을 제조하기 위해서는 아연의 응고 결정인 스팡글이 도금표면에 보이지 않도록 해야만 하는데, 이를 위한 방법으로는 상기의 조성을 갖는 통상의 용융아연 도금욕에서 도금된 용융아연 금속이 응고하기 전에 (1) 금속분말을 분사하거나, (2) 금속염 또는 무기염 수용액을 분사하여 스팡글의 핵을 무수히 만들고, 급냉에 의하여 스팡글의 성장을 억제하여 용융아연 도금강판 표면위에 실제로스팡글이 존재하나 그 크가가 미세하여 외견상 보이지 않도록 하는 방법이다.As described above, in order to manufacture a zerospangle product having no spangles on the surface of the hot-dip galvanized steel sheet, it is necessary to prevent zinc, which is a coagulation crystal of zinc, from appearing on the plating surface. Before the molten zinc metal plated in the plating bath solidifies, (1) metal powder is sprayed, or (2) metal salt or inorganic salt aqueous solution is sprayed to make the nucleus of the spangles numerous, and the growth of the spangles is suppressed by rapid cooling. Spangle is actually present on the surface of hot-dip galvanized steel sheet, but its size is so small that it is not visible.
이와 같이 제조된 제로스팡글 용융아연 도금강판에서 우수한 외관 품질의 제품에 허용되는 스팡글의 크기는 0.5mm 이하이다.The size of the spangle that is acceptable for a product of excellent appearance quality in the manufactured Jerospangle hot-dip galvanized steel sheet is 0.5 mm or less.
상기한 (1),(2)와 같은 방법으로 제로스팡글 용융아연 도금강판을 제조하기 위해 제시된 종래 방법들중 대표적인 방법으로는 일본 공개특허 공보 소49-37900호, 일본 공개특허 공보 소61-238952호, 일본 공개특허 공보 소57-26155호와 같은 방법들이 있다.Representative methods of the conventional methods proposed for producing a zerospangle hot-dip galvanized steel sheet by the same method as described above (1), (2) are Japanese Patent Laid-Open No. 49-37900, Japanese Patent Laid-Open No. 61-238952 And Japanese Laid-Open Patent Publication No. 57-26155.
상기와 같은 종래방법들중 일본 공개특허 공보 소49-37900호는 염화철과 초산철을 주제로 하고 보조제를 첨가하여 수용액을 만든 다음, 용융아연 도금강판 표면 도금층의 용융아연 금속이 응고하기 전에 상기 수용액을 분사하여 스팡글 성장을 억제하고 아연-철 합금을 도금표면층에 형성시켜 도금표면을 개선하는 방법이다.Japanese Laid-Open Patent Publication No. 49-37900 in the above conventional methods is based on iron chloride and iron acetate, and an auxiliary agent is added to make an aqueous solution, and then the aqueous solution before the molten zinc metal of the hot-dip galvanized steel sheet surface plating layer solidifies. This method is to suppress spangle growth by spraying and to form a zinc-iron alloy on the plating surface layer to improve the plating surface.
그러나, 상기 방법으로 제조된 용융아연 도금강판은 도금표면층에 함유된 철에 의해 적청이 발생하여 내식성이 불충분하고 용융아연도금강판 표면층에 국부적으로 스팡글이 잔존하는 문제점이 있다.However, the hot-dip galvanized steel sheet produced by the above method has a problem in that red blue color is generated by iron contained in the plating surface layer, so that corrosion resistance is insufficient, and spangles remain locally on the hot-galvanized steel sheet surface layer.
그리고 상기 일본 공개특허 공보 소61-238952호는 염화크롬, 초산크롬, 크롬산암모늄, 중크롬산암모늄, 유산크롬칼륨등의 열분해성 그롬계 화합물을 1종 또는 2종 이상으로 미세분말화 하여 용융아연 도금강판 표면층의 용융아연 금속이 응고하기 전에 분사하여 제로스팡글을 제조하는 방법으로서 이 방법으로 제조된 용융아연 도금강판 제품은 내식성은 우수한 반면, 분사된 분말이 불균일하게 분포되거나 또는 도금후 강판의 부위별로 온도차이가 발생시 스팡글이 잔존하는 부위가 발생하고, 국부적으로 미반응된 분말이 잔존할 경우 용융아연 도금강판 표면의 광택도에 치명적인 악영향을 주는 문제점이 있다.In Japanese Laid-Open Patent Publication No. 61-238952, a hot-dip galvanized steel sheet is obtained by finely powdering thermally decomposable gromide-based compounds such as chromium chloride, chromium acetate, ammonium chromium, ammonium dichromate and potassium chromium potassium into one or two or more kinds. As a method of manufacturing zerospangle by spraying before the molten zinc metal of the surface layer solidifies, the hot-dip galvanized steel sheet manufactured by this method has excellent corrosion resistance, but the powder is sprayed unevenly distributed or the temperature of the steel sheet after plating When the difference occurs, the site where the spangles remain, and when the locally unreacted powder remains, there is a problem that a fatal adverse effect on the gloss of the surface of the hot-dip galvanized steel sheet.
또한 상기 일본 공개특허 공보 소57-26155호는 도금욕중 A1 : 0.1-0.2wt%, Sb : 0.1-0.5wt% 조성의 도금욕에서 용융아연 도금후 강판 표면층의 용융아연 도금금속이 응고하기 전에 인산염계 무기염 수용액을 분무하여 제로스팡글 용융아연 도금을 제조하는 방법으로서, 이 방법 또한 상기 인산염계 무기염 수용액 분사시 용융아연 도금강판의 표면온도가 불균일하면 스팡글이 강판의 표면에 잔존하며, 상기 도금욕 중에 Sb의 함량이 과다하기 때문에 이 도금욕의 조성에서 레귤러 스팡글 제조시 스팡글 7-30mm 정도로 크게 성장하려는 성질이 있다.In addition, the Japanese Laid-Open Patent Publication No. 57-26155 discloses before the molten zinc plated metal of the steel sheet surface layer solidifies after hot-dip galvanizing in a plating bath composed of A1: 0.1-0.2wt% and Sb: 0.1-0.5wt% in the plating bath. A method for preparing hot-dip galvanized zinc plating by spraying an aqueous solution of phosphate-based inorganic salt, wherein the method also maintains spangles on the surface of the steel sheet when the surface temperature of the hot-dip galvanized steel sheet is uneven during spraying of the phosphate-based inorganic salt solution. Since the content of Sb in the plating bath is excessive, there is a property to grow as much as 7-30 mm spangle when manufacturing a regular spangle in the composition of this plating bath.
따라서, 인산염계 무기염 수용액을 분사하여 제로스팡글 용융아연 도금강판을 제조하기 위해서는 많은 양의 인산염계 무기염 수용액을 분사해야만 하는데, 이럴 경우 많은 양의 인산염계 무기염 수용액은 수적을 만들고, 이 수적은 용융아연 도금강판 표면에 흰색의 반점을 만들게 되어 용융아연 도금강판의 광택도에 치명적인 악영향을 주는 문제점이 있다.Therefore, in order to manufacture the ZERO-Pangle hot-dip galvanized steel sheet by injecting an aqueous solution of phosphate-based inorganic salt, a large amount of an aqueous solution of phosphate-based inorganic salt must be sprayed. There is a problem that a white spot on the surface of the hot-dip galvanized steel sheet has a fatal adverse effect on the glossiness of the hot-dip galvanized steel sheet.
상기와 같은 종래 방법들의 문제점중 특히 광택도는 도금표면의 미려함과 수요가 도장후에도 강판의 선영성에 직접적인 관계가 있기 때문에 제로스팡글 용융아연 도금강판의 품질평가시에 반드시 고려해야만 하는 중요한 항목이다.In particular, the glossiness of the conventional methods described above is an important item that must be considered when evaluating the quality of the zerospangle hot-dip galvanized steel sheet because the beauty of the plating surface and the demand have a direct relationship to the stiffness of the steel sheet even after coating.
따라서 본 발명은 상기와 같은 종래방법들의 문제점을 해결하고 광택도가 우수한 용융아연 도금강판을 제조하기 위해 제안된 것으로, 도금욕에 Sb를 첨가하여 용융아연 도금한 후 인산염계 수용액을 분사하므로서 용융아연 도금강판의 표면광택도가 우수한 고광택 제로스팡글 용융아연 도금강판 제조방법을 제공함에 그 목적이 있다.Therefore, the present invention has been proposed to solve the problems of the conventional methods as described above and to produce a hot-dip galvanized steel sheet having excellent gloss, by adding Sb to the plating bath and then hot-dip galvanizing and spraying phosphate-based aqueous solution. An object of the present invention is to provide a method of manufacturing a high-gloss zerospangle hot-dip galvanized steel sheet excellent in the surface gloss of the plated steel sheet.
이하 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명은 용융아연 도금강판의 제조방법에 있어서, 탈지 및 소둔처리된 강판을 A1 : 0.1-0.2wt%, Sb : 0.005-0.05wt%, 기타 불소원소들의 합이 0.01wt% 이하이고 잔부 Zn로 조성되는 도금욕에서 용융도금한후, 통상의 가스와이핑 처리하여 도금량을 조정한 다음, 그 농도가 1.5-2.0wt%인 인산염계 수용액을 60-100g/㎡ 분사하여 고광택 제로스팡글 용융아연 도금강판을 제조하는 방법에 관한 것이다.The present invention is a method for manufacturing a hot-dip galvanized steel sheet, the degreasing and annealing steel sheet A1: 0.1-0.2wt%, Sb: 0.005-0.05wt%, the sum of other fluorine elements is 0.01wt% or less and the balance Zn After hot-dip plating in the plating bath to be prepared, the coating amount is adjusted by the usual gas wiping treatment, and then sprayed with 60-100 g / m 2 of a phosphate-based aqueous solution having a concentration of 1.5-2.0 wt% to a high gloss zerospangle hot-dip galvanized steel sheet. It relates to a method of manufacturing.
이하 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 있어서 도금욕중 Al 농도는 0.1-0.2wt% 범위로 제한함이 바람직한데, 그 이유는 상기 도금욕중 Al의 농도가 0.1wt% 이하일 경우에는 도금층과 소지철 사이의 밀착성을 향상시키는 Fe-Al-Zn의 합금층이 생성되지 못하고 취약한 Fe-Zn의 합금층이 생성되어 가공성이 저하되며, 0.2wt% 이상일 경우에는 소지층의 Fe가 Zn 도금층으로 확산되는 것을 방해하여 합금화 용융아연 도금강판의 제조가 불가능하기 때문이다.In the present invention, the Al concentration in the plating bath is preferably limited to the range of 0.1-0.2wt%. The reason is that when the concentration of Al in the plating bath is 0.1wt% or less, the adhesion between the plating layer and the base iron is improved. Fe-Al-Zn alloy layer is not produced, weak Fe-Zn alloy layer is formed, and workability is degraded. When 0.2wt% or more, the Fe layer of the base layer prevents the diffusion of Fe into the Zn plating layer, thereby galvanizing zinc alloy. This is because the production of steel sheet is impossible.
또한, 본 발명에서는 광택특성을 나타내며, 스팡글의 성장을 발달시키는 원소인 Sb의 도금욕중 농도는 0.005-0.05wt%로 제한함이 바람직한데, 그 이유는 상기 Sb 농도가 0.005wt% 이하일 경우에는 고광택 특성을 얻을 수 없으며, 0.05wt% 이상일 경우에는 광택도는 우수하나, 스팡글을 과대성장시켜 제로스팡글 용융아연 도금강판의 제조가 불가능해질 우려가 있기 때문이다.In addition, in the present invention, it is preferable to limit the concentration in the plating bath of Sb, which exhibits glossiness and develops spangles, to 0.005-0.05 wt%, because the Sb concentration is 0.005 wt% or less. It is not possible to obtain a high gloss property, and when it is 0.05wt% or more, it is excellent in glossiness, but it may be impossible to manufacture a zerospangle hot-dip galvanized steel sheet by overgrowing the spangle.
그리고 상기 도금욕에는 Pb, Bi, Sn, Cd 등의 불소원소들이 불가피하게 함유되는데, 그 함량은 0.01wt%이하로 제한되어야만 한다. 그 이유는 상기 불순원소들의 함량이 0.01wt%를 초과할 경우에는 강판상에 스팡글이 불균일하게 성장하거나 또는 불균일하게 분포될 우려가 있기 때문이다.And the plating bath inevitably contains fluorine elements such as Pb, Bi, Sn, Cd, the content should be limited to 0.01wt% or less. The reason is that when the content of the impurity elements exceeds 0.01wt%, there is a fear that the spangles grow unevenly or unevenly distributed on the steel sheet.
한편, 본 발명은 상기와 같은 조성을 갖는 도금욕을 사용하여 용융도금한 후, 공기 또는 질소가스를 사용하여 통상의 가스와이핑 처리하여 강판의 도금부착량을 조정한 다음, 반용융상태의 용융아연 도금강판 표면의 도금층에 인산염계 수용액을 분사하여 제로스팡글화 한다.On the other hand, the present invention after the hot-dip plating using a plating bath having the composition as described above, and then adjusting the coating amount of the steel sheet by the usual gas wiping treatment using air or nitrogen gas, and then hot-dip galvanized zinc coating The phosphate-based aqueous solution is sprayed onto the plated layer on the surface of the steel sheet to be gelled.
이때, 분사하는 인산염계 수용액의 농도는 1.5-2.0wt%로 유지함이 바람직한데, 그 이유는 상기 인산염게 수용액의 농도가 1.5wt% 미만일 경우에는 냉각효과가 미흡하여 스팡글이 필요 이상으로 커질 우려가 있으며, 2.0wt%를 초과할 경우에는 인산염이 강판 표면에 잔류하여 강판의 품질이 저하될 우려가 있기 때문이다.At this time, the concentration of the sprayed phosphate-based aqueous solution is preferably maintained at 1.5-2.0wt%. The reason is that when the concentration of the phosphate aqueous solution is less than 1.5wt%, the cooling effect is insufficient and the spangle may grow larger than necessary. If the content exceeds 2.0wt%, phosphate may remain on the surface of the steel sheet, which may degrade the quality of the steel sheet.
그리고 상기와 같은 농도범위로 유지되는 인산염계 수용액을 분사시에는 도금강판 전표면에 스팡글이 생기지 않는 범위에서 최소량을 분사하는 것이 바람직하며, 이 최소분사량은 인산염계 수용액의 종류, 농도, 도금욕조성, 강판두께등에 따라 결정된다.When spraying the phosphate-based aqueous solution maintained in the concentration range as described above, it is preferable to spray the minimum amount in the range where no spangles occur on the entire surface of the plated steel sheet, and the minimum injection amount is the type, concentration, and plating bath of the phosphate-based aqueous solution. It depends on the composition, steel sheet thickness, and the like.
본 발명에서는 인산염계 수용액으로 인산수소 암모늄과 인산수소 나트륨을 사용하였으며, 그 분사량은 60-100g/㎡로 제한하였다. 그 이유는 상기 인산염계 수용액의 분사량이 60g/㎡ 이하일 경우에는 냉각효과가 미흡하여 스팡글이 과대성장하여 조대해지며, 100g/㎡ 이상일 경우에는 수적이 발생하고, 이 수적이 도금강판 표면에 떨어져 흰반점을 만들어 광택도를 저하시키기 때문이다.In the present invention, ammonium hydrogen phosphate and sodium hydrogen phosphate were used as the phosphate-based aqueous solution, and the injection amount was limited to 60-100 g / m 2. The reason for this is that when the injection amount of the phosphate-based aqueous solution is 60 g / m 2 or less, the cooling effect is insufficient, and the spangles grow excessively and become coarse. When 100 g / m 2 or more, water drops occur, and the water drops fall on the plated steel sheet surface. This is because white spots are created to reduce gloss.
상술한 바와 같은 본 발명의 방법을 사용하여 강판을 용융아연 도금할 경우에는 용융아연 도금된 강판의 폭 및 길이방향으로 온도 구배가 발생하더라도 용융아연 도금강판 전표면에 걸쳐 스팡글 발생을 억제할 수 있다. 그 이유는 도금욕중 불순원소의 함량을 최소로 관리하여 도금욕의 순도를 높이고 스팡글을 성장 발달시키는 Sb 함량을 0.005-0.05wt% 범위로 관리하므로서 도금후 자연냉각하여도 스팡글이 성장할 수 있는 최대의 크기를 3mm 이내로 억제하고, 스팡클 발생직전의 반용융상태의 용융아연 도금표면에 저온에서도 열분해가 용이하고 열분해시 흡열량이 많아 냉각효과가 높은 1.5-2.0wt% 농도의 인산염계 수용액을 60-100g/㎡ 범위내로 분사하므로서 용이하게 제로스팡글화 할 수 있기 때문이다.When hot-dip galvanizing the steel sheet using the method of the present invention as described above, even if a temperature gradient occurs in the width and length direction of the hot-dip galvanized steel sheet, it is possible to suppress the generation of spangles over the entire surface of the hot-dip galvanized steel sheet. have. The reason is that it manages the content of impurity elements in the plating bath to the minimum to increase the purity of the plating bath and manage the Sb content in the range of 0.005-0.05wt% so that spangles can grow even after cooling naturally after plating. It is possible to suppress the maximum size within 3mm, and easy to thermal decomposition at low temperature on the surface of semi-melt molten zinc plating just before the generation of spackle, and to have a large amount of heat absorption during thermal decomposition. This is because it can be easily zerospangle by spraying within the range of 60-100g / ㎡.
또한, 본 발명의 방법으로 제조된 용융아연 도금강판이 고광택특성을 갖는 것은 도금욕내에 광택특성을 나타내며, 스팡글을 성장시키는 원소인 Sb : 0.005-0.05wt% 농도범위로 함유시키므로서 도금층내에 Sb가 충분히 포함되고, 또한 스팡글의 최대성장 크기를 3mm 이내로 억제하므로서 1.5-2.0wt% 농도의 인산염계 수용액을 60-100g/㎡ 범위로 분사하여도 제로스팡글 용융아연 도금강판을 용이하게 제조할 수 있어 도금층 표면에 수적이 발생치 않기 때문이다.In addition, the hot-dip galvanized steel sheet produced by the method of the present invention has a high gloss property, exhibits glossiness in the plating bath, and contains Sb in a concentration range of 0.005-0.05 wt%, which is an element to grow spangles, and Sb in the plating layer. Is sufficiently contained, and while suppressing the maximum growth size of the spangle to within 3mm, even when spraying a 1.5-2.0wt% phosphate-based aqueous solution in the range of 60-100g / ㎡ can be easily produced zerospangle hot-dip galvanized steel sheet This is because water droplets do not occur on the surface of the plating layer.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
(실시예)(Example)
용융아연 도금설비에서 0.6mm의 저탄소 강판을 150m/min의 라인속도로 알칼리 탈지하고 무산화로 및 환원로에서 소둔을 행한 다음, 465+5℃의 도금온도에서 하기표 1의 조성을 갖는 도금욕에서 용융아연 도금후, 가스와이핑 처리하여 용융아연 도금된 강판 양면의 도금량을 180g/㎡으로 조정하였다.In a hot dip galvanizing facility, a 0.6 mm low carbon steel sheet was alkali degreased at a line speed of 150 m / min and annealed in an anhydrous furnace and a reduction furnace, and then melted in a plating bath having the composition shown in Table 1 at a plating temperature of 465 + 5 ° C. After galvanizing, gas wiping was performed to adjust the plating amount on both sides of the hot dip galvanized steel sheet to 180 g / m 2.
그리고 상기와 같이 조정된 반용융상태의 용융아연 도금층에 하기표 1과 같이 각 도금욕 성분에 있어서 최적의 분사량으로 인산염계 수용액을 분사하거나 또는 5μm 이하의 아연분말을 분사하여 제로스팡글화 하였다.Then, phosphate-based aqueous solution was sprayed on the semi-melted zinc coating layer adjusted as described above at the optimum spraying amount in each plating bath component as shown in Table 1 below, or by spraying zinc powder of 5 μm or less.
상기와 같이 제조된 용융아연 도금강판의 표면외관, 스팡글크기, 광택도를 측정하고, 그 결과를 하기표 1에 나타내었다.The surface appearance, the spangle size, and the glossiness of the hot-dip galvanized steel sheet prepared as described above were measured, and the results are shown in Table 1 below.
[표 1]TABLE 1
* 주; 1) 표면외관* Note; 1) Surface appearance
○ : 우수(백색반점이나 분말이 없으며 평활하고 빛이 남)○: Excellent (no white spots or powder, smooth and light)
△ : 보통(부분적으로 백색반점이나 미반응 분말이 존재)(Triangle | delta): Normal (partly white spot or unreacted powder exists)
× : 불량(전면에 백색반점이나 미반응 분말이 발생 )X: Poor (white spot or unreacted powder is generated on the front)
2) 스팡글 크기2) Spangle Size
○ : 우수(용융아연 도금강판 전표면의 스팡글의 크기가 0.5mm 이하임)○: Excellent (Spangle of the entire surface of molten zinc plated steel sheet is 0.5mm or less)
△ : 보통(스팡글 크기가 0.5mm 이하이나 부분적으로 2-3mm의 스팡글이 존재함)△: Normal (Spangle size is 0.5mm or less but partially 2-3mm spangle exists)
× : 불량(스팡글의 크기가 0.5mm 이상이고 2-3mm의 스팡클이 불균일하게 나타남)×: Poor (spangle is 0.5mm or more and 2-3mm spankle appears unevenly)
3) 광택도3) glossiness
00 : 극히 우수(JIS Z 8741에 의해 20°에서 측정한 광택도가 200 이상)00: Extremely excellent (more than 200 glossiness measured at 20 ° by JIS Z 8741)
○ : 우수(20°에서 측정한 광택도가 100-200 미만)○: excellent (gloss measured at 20 ° less than 100-200)
△ : 보통(20°에서 측정한 광택도가 50-100 미만)(Triangle | delta): Moderate (The glossiness measured at 20 degrees is less than 50-100)
× : 불량(20°에서 측정한 광택도가 50 미만)X: Poor (gloss less than 50 measured at 20 °)
4)Tr : 상기 표 1에서 Tr은 화학적으로 분석되지 않는 극소량을 나타냄4) Tr: In Table 1, Tr represents a very small amount that is not chemically analyzed.
상기 표 1에 나타난 바와 같이 본 발명의 도금욕 조성과 인산염계 수용액 분자량 범위를 만족하는 발명예(1-8)는 본 발명의 범위로 벗어나는 비교예(9-19)와 비교하여 볼 때 표면외관과 스팡글 크기에 있어서는 동등이상의 효과를 나타내며, 특히 광택도에 있어서는 월등한 효과를 나타냄을 알 수 있다.As shown in Table 1, the Inventive Example (1-8) satisfying the plating bath composition and the phosphate-based aqueous solution molecular weight range of the present invention has a surface appearance when compared with the Comparative Example (9-19) which deviates from the scope of the present invention. It can be seen that the effect is equal to or higher in the size of and the spankle, and in particular, the effect is excellent in the glossiness.
상술한 바와 같이, 본 발명은 도금욕중 Al, Sb의 농도를 관리하고, 불순원소들의 함량을 미량으로 제한하여 도금욕의 순도를 높여 용융아연도금을 한 후, 인산염계 수용액을 반용융상태의 용융아연 도금강판 표면에 분사하므로서 용융아연 도금강판의 표면외관이 우수하고, 스팡글의 크기가 0.5mm 이하로 미세할 뿐만 아니라 특히 광택도에 있어서 월등한 효과가 있다.As described above, the present invention manages the concentration of Al, Sb in the plating bath, limits the content of impurities in a small amount to increase the purity of the plating bath after hot-dip galvanizing, phosphate-based aqueous solution in a semi-molten state By spraying on the surface of the hot-dip galvanized steel sheet, the surface appearance of the hot-dip galvanized steel sheet is excellent, and the size of the spangle is not more than 0.5 mm, and the gloss is particularly excellent.
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| KR100833031B1 (en) * | 2001-12-22 | 2008-05-27 | 주식회사 포스코 | A method for manufacturing Tin plated steel sheet |
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| KR100425594B1 (en) * | 1999-12-14 | 2004-04-03 | 주식회사 포스코 | Solution spray for minimized spangle |
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| KR100833031B1 (en) * | 2001-12-22 | 2008-05-27 | 주식회사 포스코 | A method for manufacturing Tin plated steel sheet |
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