KR20100124436A - Hot dip zn-based alloy coating bath, hot dip zn-based alloy coated steel and method for manufacturing the same - Google Patents
Hot dip zn-based alloy coating bath, hot dip zn-based alloy coated steel and method for manufacturing the same Download PDFInfo
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- KR20100124436A KR20100124436A KR1020090043437A KR20090043437A KR20100124436A KR 20100124436 A KR20100124436 A KR 20100124436A KR 1020090043437 A KR1020090043437 A KR 1020090043437A KR 20090043437 A KR20090043437 A KR 20090043437A KR 20100124436 A KR20100124436 A KR 20100124436A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 86
- 239000010959 steel Substances 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 23
- 229910045601 alloy Inorganic materials 0.000 title abstract description 27
- 239000000956 alloy Substances 0.000 title abstract description 27
- 239000011248 coating agent Substances 0.000 title abstract 2
- 238000000576 coating method Methods 0.000 title abstract 2
- 238000007747 plating Methods 0.000 claims abstract description 105
- 239000000463 material Substances 0.000 claims abstract description 55
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 19
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 14
- 239000010960 cold rolled steel Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 10
- 239000008397 galvanized steel Substances 0.000 claims description 10
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 9
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- -1 zinc-aluminum-magnesium Chemical compound 0.000 claims description 6
- 238000005246 galvanizing Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 230000003746 surface roughness Effects 0.000 abstract description 8
- 229910000677 High-carbon steel Inorganic materials 0.000 abstract description 2
- 238000003287 bathing Methods 0.000 abstract description 2
- 235000012907 honey Nutrition 0.000 description 38
- 238000005260 corrosion Methods 0.000 description 35
- 230000007797 corrosion Effects 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 21
- 238000005452 bending Methods 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229940062057 nitrogen 80 % Drugs 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018084 Al-Fe Inorganic materials 0.000 description 1
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018192 Al—Fe Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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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
- C23C2/04—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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
-
- 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
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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)
- Coating With Molten Metal (AREA)
Abstract
Description
본 발명은 건축자재용, 가전용, 자동차용 등에 사용되는 도금강재에 관한 것으서, 보다 상세하게는 내식성과 굽힘가공성을 향상시키기 위해서 사용되는 용융 아연합금 도금욕, 이를 이용한 용융 아연합금 도금강재의 제조방법 및 상기 방법으로 제조된 용융 아연합금 도금강재에 관한 것이다.The present invention relates to a plated steel used for building materials, home appliances, automobiles, and the like, and more particularly to a plated steel material used for improving corrosion resistance and bending workability, and a hot-dip galvanized steel sheet And a hot-dip galvanized steel produced by the method.
종래부터 강재의 표면에 아연 도금을 실시하여 강재의 내식성을 개선하는 것은 널리 알려져 왔고, 현재까지도 아연 도금된 강재는 대량 생산되어 사용되고 있다.BACKGROUND ART It has hitherto been widely known to improve the corrosion resistance of a steel material by applying zinc plating to the surface of the steel material. To date, zinc-plated steel materials have been mass-produced and used.
그러나 건축자재, 가전, 자동차 등 다양한 용도에 사용되기 위해서, 상기와 같은 아연 도금만으로는 내식성이 불충분한 문제가 있다. 따라서 도금층의 내식성을 향상시킬 수 있도록 알루미늄을 첨가한 용융 아연-알루미늄합금 도금강재, 예를 들면, 55%알루미늄-아연을 이용한 용융 아연-알루미늄합금 도금강재을 사용하고 있 다. 그러나 상기 용융 아연-알루미늄합금 도금강재은 벌크(bulk) 도금층의 알루미늄 함량이 아연에 비하여 많기 때문에, 희생 방식(sacrificial corrosion prevention)능력이 저하되고, 도금된 재료에서의 단면과 같은 소지금속(underlying metal)이 노출되는 부분에서 부식이 생기는 문제가 남는다. However, in order to be used in various applications such as building materials, home appliances, and automobiles, there is a problem in that corrosion resistance is insufficient only by the above-described zinc plating. Therefore, a hot-dip zinc-aluminum alloy plated steel, for example, a hot-dip zinc-aluminum alloy plated steel using 55% aluminum-zinc is used to improve the corrosion resistance of the plated layer. However, since the molten zinc-aluminum alloy plated steel material has a higher aluminum content of the bulk plating layer than zinc, sacrificial corrosion prevention ability is lowered and the underlying metal such as a cross section in the plated material is lowered. There is a problem that corrosion occurs at the exposed portion.
또한 상기 55%알루미늄-아연 도금을 할 때, 도금욕의 온도를 600℃ 정도로 높게 설정해야 하기 때문에 도금층의 가공성이 열악하며, 도금욕내 각종 구조부위의 설비에 부식이 발생하는 문제로 인해, 설비의 수명이 짧아지며 설비 교체에 따른 생산성이 낮아지는 문제점이 있다.In addition, when the above-mentioned 55% aluminum-zinc plating is performed, the plating bath has to be set at a high temperature as high as about 600 ° C., so that the processability of the plating layer is poor and corrosion occurs in facilities of various structural parts in the plating bath. The life span is shortened and the productivity due to the replacement of the equipment is lowered.
한편 아연-알루미늄합금 도금강재에 대한 종래의 기술을 살펴보면 다음과 같다.Meanwhile, a conventional technique for zinc-aluminum alloy plated steel will be described as follows.
국제공개특허 WO2007/146161에서는 일반 용융아연도금을 위한 고알루미늄(10~40%)의 합금 용융아연도금이 개시되어 있다. 상기 특허에서는 아연-암모늄 플럭스에 침적시킨 뒤 실리콘을 포함하는 아연-알루미늄 도금욕에서 도금을 실시하는 이른바 플럭스 아연도급법을 제시하고 있다. 그러나 상기 플럭스 아연도금법은 주로 구조물, 파이프 등 단위 부품을 단속적으로 도금하는데 적용되며, 강재를 연속적으로 도금하는 방법으로는 전처리 공정이 상이하고, 도금 부착량 제어 및 표면 품질의 관리 측면에서 적용이 어렵게 된다.WO2007 / 146161 discloses high-alloy (10-40%) hot-dip galvanizing for general hot dip galvanizing. The above patent discloses a so-called flux-zinc plating method in which plating is carried out in a zinc-aluminum plating bath containing silicon and then immersed in a zinc-ammonium flux. However, the flux zinc plating method is mainly applied to intermittently plating unit parts such as a structure and a pipe, and the method of continuously plating the steel material is different from the pretreatment step, and it is difficult to apply the method in terms of plating amount control and surface quality management .
한편 일본을 중심으로 개발된 아연-알루미늄-마그네슘 도금강재은 강재의 표면에 알루미늄상을 포함한 아연-마그네슘상(Zn11Mg2)이 국부적으로 존재하면 변색되기 쉽고, 이를 방치하면 이 부분이 두드러진 색조로 되어 표면외관을 현저히 저하시킨다. 또한 제품 폭방향으로 연장되는 선상의 줄무늬가 발생하여 도금 후 냉각속도를 조정하거나 특수원소를 도금욕에 첨가하여야 하는 문제점을 가진다.On the other hand, the zinc-aluminum-magnesium plated steel material developed mainly in Japan is likely to be discolored when the zinc-magnesium phase (Zn 11 Mg 2 ) containing the aluminum phase locally exists on the surface of the steel material. And the surface appearance is remarkably lowered. There is a problem that line-shaped stripes extending in the width direction of the product are generated to adjust the cooling rate after plating or add special elements to the plating bath.
또한 유럽특허번호 제1621645호와 같이, 유럽을 중심으로 개발되고 있는 또다른 형태의 아연-알루미늄-마그네슘 합금 도금강재는 알루미늄과 마그네슘의 첨가총량이 일본에서 개발된 아연-알루미늄-마그네슘 합금 도금강재보다 적어 내식성이 충분히 확보되지 않는 문제점이 있다. Another type of zinc-aluminum-magnesium alloy plated steel which is being developed mainly in Europe, such as the European Patent No. 1621645, is that the total amount of aluminum and magnesium added is higher than that of the zinc-aluminum-magnesium alloy plated steel material developed in Japan There is a problem that sufficient corrosion resistance is not ensured.
따라서 자동차뿐만 아니라, 건축자재, 가전 등 다양한 용도에 적용될 수 있도록 내식성 및 굽힘 가공성이 우수한 도금강재이 요구되고 있으며, 이를 위한 도금욕 성분 및 도금방법이 요구되고 있다.Therefore, there is a demand for a plated steel material excellent in corrosion resistance and bending workability so that it can be applied not only to automobiles, but also to various uses such as building materials, home appliances, etc., and a plating bath component and a plating method therefor are required.
본 발명의 일측면에 따르면 내식성 및 굽힘가공성이 우수한 도금강재를 제공하기 위해서, 도금시 도금욕의 온도를 낮출 수 있는 용융 아연합금 도금욕, 이를 이용한 용융 아연합금 도금강재의 제조방법 및 상기 방법으로 제조된 용융 아연합금 도금강재가 제공된다.According to one aspect of the present invention, there is provided a molten zinc alloy plating bath capable of lowering the temperature of a plating bath at the time of plating in order to provide a plated steel having excellent corrosion resistance and bending workability, a method of producing a molten zinc alloy plated steel using the same, A prepared hot-dip zinc alloy plated steel is provided.
본 발명은 중량%로, 알루미늄(Al): 10~30%, 실리콘(Si): 0.01~0.5%, 마그네슘(Mg): 0.1~3%, 미슈메탈: 0.1~0.5%를 포함하고 나머지는 아연 및 불가피한 불순물로 조성되는 용융 아연합금 도금욕을 제공한다.The present invention is characterized by containing 10-30% of aluminum (Al), 0.01-0.5% of silicon (Si), 0.1-3% of magnesium (Mg), and 0.1-0.5% of misch metal, And an inevitable impurity.
또한 본 발명은 강재를 전처리하는 단계;The present invention also provides a method of manufacturing a steel sheet,
상기 전처리된 강재를 열처리하는 단계; 및Heat treating the pretreated steel material; And
상기 열처리된 강재를 상기 용융 아연합금 도금욕에 통과시켜 도금하는 단계를 포함하는 용융 아연합금 도금강재의 제조방법을 제공한다.And a step of passing the heat treated steel material through the molten zinc alloy plating bath and plating the molten zinc alloy plated steel material.
또한 본 발명은 상기 제조방법에 의해 제조된 용융 아연합금 도금강재를 제공한다.The present invention also provides a hot-dip galvanized steel material produced by the above-mentioned production method.
본 발명은 알루미늄-아연 도금욕에 실리콘과 미슈메탈을 첨가하여 도금층 단면에 합금층이 거의 제거됨으로써 표면조도가 평활해지고 광택도가 균일해지며, 도금층의 굽힘 밀착성이 양호해짐에 따라 표면외관 특성과 내식성이 향상되는 효과를 갖는다. 또한 마그네슘을 첨가하여 도금층 표면외관이 양호하면서 도금특성이 우수하며 특히 도금층 내식성이 더욱 향상됨을 알 수 있다. 또한 본 발명에 의하면 아연-알루미늄-마그네슘의 3원합금 도금시 도금공정의 온도를 낮출 수 있음에 따라 도금욕 구조부위들의 용출이 억제되고, 그 결과 부품의 수명이 길어지고 교체주기가 연장되면서 생산성 향상의 효과를 얻을 수 있다.In the present invention, silicon and mischmetal are added to an aluminum-zinc plating bath so that the alloy layer is almost removed from the end face of the plating layer, so that the surface roughness becomes smooth and the gloss becomes uniform. As the plating adhesion of the plating layer becomes better, And the corrosion resistance is improved. In addition, magnesium is added to provide a good appearance on the surface of the plating layer, and the plating property is excellent. In particular, the corrosion resistance of the plating layer is further improved. In addition, according to the present invention, since the temperature of the plating process can be lowered when plating the ternary alloy of zinc-aluminum-magnesium, the elution of the plating bath structure portions is suppressed. As a result, The effect of improvement can be obtained.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
먼저, 용융 아연합금 도금욕의 조성에 대하여 상세히 설명한다(이하, 중량%)First, the composition of the molten zinc alloy plating bath will be described in detail (hereinafter, "wt%")
본 발명의 일측면인 용융 아연합금 도금욕은 중량%로, 알루미늄(Al): 10~30%, 실리콘(Si): 0.01~0.5%, 마그네슘(Mg): 0.1~3%, 미슈메탈: 0.1~0.5%를 포함하고 나머지는 아연 및 불가피한 불순물로 이루어진다.The molten zinc alloy plating bath, which is one aspect of the present invention, comprises 10 to 30% of aluminum (Al), 0.01 to 0.5% of silicon (Si), 0.1 to 3% of magnesium (Mg) To 0.5%, the balance being zinc and inevitable impurities.
알루미늄(Al)은 고내식성 확보를 위해서 첨가된다. 도금욕 중 알루미늄 첨가량이 증가하면 도금강재의 내식성이 증가하는데, 이는 알루미늄이 도금층 중 알루미늄 산화피막으로 존재하여 산화환원 반응이 억제되고, 그에 상응하는 양극반응인 아연 용출속도가 낮아지기 때문이다. 즉, 부식초기 생성된 부식생성물 피막이 도금 표면을 덮어 합금원소의 역할로서 부식생성물의 전도도가 낮은 수산화 아연으로 유지되고, 이에 산화아연의 전도성이 저하됨으로써 산화환원 반응이 억제된다. 본 발명에서 Al의 함량을 10~30%로 한정한 이유는 그 함량이 10% 미만에서는 합금 도금 층에서의 내식성이 저하되며, 30% 초과에서는 드로스 발생량이 증가하여 도금욕 관리가 어렵게 되고 표면외관이 열화되기 때문이다.Aluminum (Al) is added to ensure high corrosion resistance. When the amount of aluminum added in the plating bath is increased, the corrosion resistance of the plated steel is increased because the aluminum is present as an aluminum oxide film in the plating layer to suppress the redox reaction, and the zinc elution rate corresponding to the anode reaction is lowered. That is, the corrosion product film formed at the early stage of corrosion covers the surface of the plating to maintain the conductivity of the corrosion product as zinc hydroxide as a role of the alloying element, and the conductivity of the zinc oxide is lowered, thereby suppressing the redox reaction. The reason for limiting the content of Al in the present invention to 10 to 30% is that when the content is less than 10%, corrosion resistance in the alloy plating layer is deteriorated. When the content exceeds 30%, the amount of dross is increased, This is because the appearance is deteriorated.
실리콘(Si)은 표면조직에서의 파우더링 현상과 단면조직에서의 합금층 성장을 방지하기 위해서 첨가된다. 실리콘은 주로 소지철/도금층 계면에 존재하면서 소지철에서 도금층으로 확산하는 철량을 감소시키고 도금층에서 소지철로 확산하는 알루미늄량을 감소시킨다. 이러한 실리콘 첨가 효과에 의해 합금층 두께가 감소되면서 굽힘 밀착성이 향상되는데, 그 함량이 0.01% 이상 첨가하면 합금층 억제 효과가 나타나기 시작하고 0.5% 이상 첨가되면 그 효과가 현저해진다. 그럼에도 불구하고 실리콘 함량을 0.01∼0.5%로 한정한 이유는 그 함량이 0.01% 미만에서는 합금층 생성 억제효과가 미약하며, 도금층 굽힘 밀착성이 열화되는 반면, 0.5% 초과에서는 도금층 가공성, 표면외관 등의 특성에서 더 이상의 향상 효과가 나타나지 않기 때문이다.Silicon (Si) is added to prevent the powdering phenomenon in the surface texture and the alloy layer growth in the cross-section structure. Silicon reduces the amount of iron diffusing from the base iron to the plating layer while reducing the amount of aluminum diffusing from the plating layer to the base iron, while being present mainly at the base iron / plated layer interface. The effect of silicon addition decreases the alloy layer thickness and improves the bending adhesion. When the content is more than 0.01%, the alloy layer suppressing effect begins to appear. When the content is more than 0.5%, the effect becomes remarkable. Nevertheless, the reason for limiting the silicon content to 0.01 to 0.5% is that when the content is less than 0.01%, the effect of inhibiting the formation of the alloy layer is weak and the bending adhesion of the plating layer is deteriorated. On the other hand, No further improvement in the properties is seen.
미슈메탈(Mischmetal)은 약 90%의 희토류 원소(REM)와 약 10%의 철(Fe)의 합금으로 철강의 첨가제 및 발화합금의 원료로써 이용되어 왔다. 본 발명에서 미슈메탈은 도금층/소지철 계면에 석출하여 계면층을 안정화시키는 역할을 하며 도금층을 평활하게 한다. 그러나 도금욕 온도가 상승하면 금속간 화합물 형성속도와 성장속도가 증가하여 취약한 철-알루미늄 합금층을 형성한다. 본 발명에서 미슈메탈은 0.1∼0.5% 범위로 첨가되는데 0.1% 미만으로 첨가되면 강재와 도금욕의 젖음성 향 상 효과를 얻을 수 없어 도금층 표면이 거칠게 되기 쉽고 0.5% 초과하여 첨가되면 과도한 금속 산화물 생성으로 인하여 도금표면 외관이 열화되는 경향을 나타낸다.Mischmetal is an alloy of about 90% rare earth element (REM) and about 10% iron (Fe) and has been used as a raw material for steel additives and ignition alloys. In the present invention, mischmetal precipitates on the plating layer / substrate iron interface to stabilize the interface layer and smooth the plating layer. However, when the plating bath temperature rises, intermetallic compound formation rate and growth rate increase to form a weak iron-aluminum alloy layer. In the present invention, mischmetal is added in the range of 0.1 to 0.5%, and if it is added in an amount of less than 0.1%, the wettability of the steel and the plating bath can not be improved and the surface of the plating layer is easily roughened. The surface appearance of the plating surface tends to deteriorate.
본 발명에서 사용되는 미슈메탈은 제한되지 않는다. 한가지 바람직한 미슈메탈의 예로는 La-rich 미슈메탈이 있으며, 이는 La: 50중량%, Ce: 25중량%, Nd: 8~15중량%, Pr: 3~7중량%, 나머지는 Fe로 이루어진다.The mischmetal used in the present invention is not limited. An example of a preferred mischmetal is La-rich mischmetal, which comprises 50% by weight of La, 25% by weight of Ce, 8-15% by weight of Nd, 3 to 7% by weight of Pr and the balance of Fe.
마그네슘(Mg)은 도금욕내 마그네슘을 첨가하면 산화아연 형성반응을 억제하고 부식초기 단계에서 용출된 마그네슘이 수산화아연 혹은 산화아연에 스며들어 염기성 염화아연으로 변화하여 더 이상의 녹 발생을 억제하는 효과가 있다. 마그네슘은 도금층 및 절단면의 내식성 향상을 위하여 0.1∼3.0% 범위에서 첨가하는데 0.1% 미만에서는 내식성 향상효과가 미미하며, 3.0% 초과하여 첨가하면 도금욕이 산화되기 쉽고 드로스 발생량이 증가하여 조업성을 저해하기 때문이다.Magnesium (Mg) has the effect of suppressing the formation of zinc oxide by adding magnesium in the plating bath, and the magnesium eluted in the early stage of corrosion penetrates into zinc hydroxide or zinc oxide and changes into basic zinc chloride, thereby suppressing further generation of rust . Magnesium is added in the range of 0.1 to 3.0% for the purpose of improving the corrosion resistance of the plating layer and the cut surface. When it is less than 0.1%, the effect of improving the corrosion resistance is insignificant. When it is added by more than 3.0%, the plating bath is easily oxidized and the amount of dross is increased. It is because it inhibits.
본 발명에서는 상기 알루미늄(Al)과 실리콘(Si)의 함량이 30≤Al/Si≤120의 관계를 만족하는 것이 바람직하다.In the present invention, it is preferable that the content of aluminum (Al) and silicon (Si) satisfy the relation of 30? Al / Si? 120.
전술한 바와 같이, 알루미늄은 도금강재의 내식성을 증가시키는 역할을 하며, 실리콘은 소지철과 도금층에서의 철과 알루미늄의 확산을 감소시켜 굽힘밀착성을 향상시키는 역할을 한다. 이때 실리콘이 과도하게 첨가되어 Al/Si의 값이 30 미만이면 나내식성이 열위에 있게되고, 120을 초과하게 되면 굽힘밀착성이 열위에 있는 문제가 있다. As described above, aluminum serves to increase the corrosion resistance of the plated steel, and silicon serves to improve the bending adhesion by reducing the diffusion of iron and aluminum in the ferrous and plated layers. At this time, when the silicon is excessively added and the value of Al / Si is less than 30, the corrosion resistance is in the hot state, and when it exceeds 120, there is a problem that the bending adhesion is inferior.
나머지는 아연(Zn) 및 불가피한 불순물로 이루어진다.The remainder consists of zinc (Zn) and inevitable impurities.
이하, 상기 용융 아연합금 도금욕을 이용하여 용융 아연합금 도금강재를 제조하는 방법에 대하여 상세히 설명한다.Hereinafter, a method for manufacturing a molten zinc alloy plated steel material by using the molten zinc alloy plating bath will be described in detail.
본 발명에 적용되는 강재는 제한은 없으나 바람직하게는 저탄소강, 극저탄소강 및 고탄소강 중 어느 하나를 사용한다. 또한 본 발명에 적용되는 강재는 열연강재 또는 냉연강재가 사용된다. 상기 열연강재는 1.0~4.0㎜의 두께를 갖는 것이 바람직하며, 냉연강재는 0.3~2.3㎜의 두께를 갖는 것이 바람직하다.The steel material used in the present invention is not limited, but preferably one of low carbon steel, ultra low carbon steel and high carbon steel is used. The steel material to be used in the present invention may be hot rolled steel or cold rolled steel. The hot-rolled steel material preferably has a thickness of 1.0 to 4.0 mm, and the cold-rolled steel material preferably has a thickness of 0.3 to 2.3 mm.
본 발명의 강재를 용융 아연합금 도금하기 위해서는 먼저, 전처리공정(Pre-treatment or Pre-cleaning)을 수행하여 강재의 표면을 세정한다. In order to coat the steel material of the present invention with a molten zinc alloy, the surface of the steel material is first cleaned by performing a pre-treatment or a pre-cleaning.
상기 전처리공정에는 산세, 수세, 탈지 등의 공정이 포함된다. 열연강재의 도금성 향상을 위하여 전처리 조건이 중요하며 바람직하게는 스케일 제거를 위한 산세처리가 필요하다. 냉연강재는 탈지처리를 하는 것이 바람직하다.The pretreatment step includes a step of pickling, washing, degreasing and the like. Pretreatment conditions are important for improving the plating performance of hot-rolled steel, and pickling treatment for scale removal is preferably required. The cold-rolled steel is desirably degreased.
상기 전처리 공정을 거친 강재를 도금욕에 통과시키기 전에 열처리공정을 수행한다. 상기 열처리는 환원분위기에서 행하는 환원 열처리가 바람직하고, 통상의 방법에 의하며 충분하다. 한가지 바람직한 예를 든다면, 이슬점 온도가 -40℃인 수소 20%-질소 80%의 분위기에서 행한다.A heat treatment process is performed before passing the pre-treated steel through a plating bath. The heat treatment is preferably a reduction heat treatment performed in a reducing atmosphere, and it is sufficient by a usual method. In one preferred embodiment, the reaction is carried out in an atmosphere of 20% hydrogen and 80% nitrogen at a dew point temperature of -40 ° C.
상기 열처리공정은 열연강재 또는 냉연강재를 사용하는지에 따라 그 온도범위가 달라지는 바, 이하 열연강재와 냉연강재를 달리하여 설명한다.The temperature range varies depending on whether a hot-rolled steel sheet or a cold-rolled steel sheet is used. Hereinafter, the hot-rolled steel sheet and the cold-rolled steel sheet will be described in detail.
열연강재를 도금하는 경우의 열처리 공정에 대하여 상세히 설명한다. The heat treatment process for plating hot-rolled steel will be described in detail.
열연강재는 냉연강재와 비교하여 표면특성이 상이하고 소재의 재질 확보와 도금층 굽힘 밀착성 확보를 위하여 적정 열처리 조건이 요구된다. 연속도금에 있어 열연강재는 본래의 재질을 유지하기 위하여 가능한 낮은 온도로 가열하는 것이 필요하므로 강재를 도금욕 온도와 유사하게 가열하여 도금하는 것이 바람직하며, 이는 저탄소, 극저탄소, 고강도강 모두 동일하게 적용된다. 이때의 온도는 500~600℃가 바람직하다. The hot-rolled steel has different surface characteristics compared to cold-rolled steel, and proper heat treatment conditions are required for securing the material and securing the adhesion of the plating layer to the bend. In continuous plating, it is desirable to heat the hot-rolled steel to a temperature as low as possible in order to maintain the original material, so it is preferable to heat the steel by heating in a manner similar to the plating bath temperature. This is preferable because the low- . The temperature at this time is preferably 500 to 600 ° C.
이하 압연된 상태의 냉연강재를 도금하는 경우의 열처리 공정에 대하여 상세히 설명한다.Hereinafter, the heat treatment process in the case of rolling the cold rolled steel material in a rolled state will be described in detail.
냉연강재는 압연된 강재의 표면을 세정하는 전처리 공정과 열처리 후 도금 및 후처리 공정으로 구별된다. 탈지 등 전처리 후 압연조직의 회복, 재결정소둔을 위하여 열처리를 실시하는데 일반 저탄소강은 700~800℃로, 극저탄소강과 고강도강은 800~850℃로 각각 가열하는 열처리 과정을 수행한다. Cold rolled steel is distinguished by a pretreatment process for cleaning the surface of rolled steel and a post-heat treatment plating and post-treatment process. After the pretreatment such as degreasing, heat treatment is performed for recovery of the rolled structure and annealing for recrystallization. In general low carbon steel is subjected to heat treatment at 700 to 800 ° C, ultra low carbon steel and high strength steel at 800 to 850 ° C.
상기와 같이 전처리 공정 및 열처리 공정을 거친 강재를 전술한 용융 아연합 금 도금욕에 통과시켜 도금한다. 상기 도금은 연속적으로 행하는 것이 바람직하다.The steel material subjected to the pretreatment process and the heat treatment process as described above is passed through the above-mentioned molten alloy-coupled gold plating bath to perform plating. The plating is preferably performed continuously.
이때 상기 강재의 입욕온도는 500~600℃로 관리하고, 상기 용융 아연합금 도금욕 온도는 500~550℃로 관리한다.At this time, the bath temperature of the steel is controlled at 500 to 600 ° C, and the temperature of the hot-dip galvanizing bath is controlled at 500 to 550 ° C.
상기 강재의 입욕온도와 도금욕 온도는 도금층 외관과 도금층 밀착성 확보를 위한 것으로써, 도금욕의 온도가 500℃ 미만에서는 도금표면에서의 미도금 현상이 관찰되면서 밀착성이 열화되며 도금욕의 온도가 550℃ 초과에서는 도금층 크랙이 증가하면서 밀착성이 나빠지므로 도금욕 온도를 500∼550℃로 관리하는 것이 바람직하다. When the temperature of the plating bath is less than 500 ° C., the plating is undeveloped on the surface of the plating, and the adhesion is deteriorated. When the temperature of the plating bath is 550 Lt; 0 > C, cracking of the plating layer is increased and adhesion is deteriorated. Therefore, it is preferable to control the plating bath temperature to 500 to 550 deg.
이하 본 발명인 상기 도금욕 및 제조방법에 의하여 제조된 용융 아연합금 도금강재에 대하여 상세히 설명한다. Hereinafter, the plating bath of the present invention and the hot-dip galvanized steel material produced by the manufacturing method will be described in detail.
상기 용융 아연합금 도금강재는 중량%로, 알루미늄(Al): 10~30%, 실리콘(Si): 0.01~0.5%, 마그네슘(Mg): 0.1~3%, 미슈메탈: 0.1~0.5%를 포함하고 나머지는 아연 및 불가피한 불순물로 이루어지는 도금층을 포함한다. 바람직하게는 상기 알루미늄(Al)과 실리콘(Si)의 함량이 30≤Al/Si≤120의 관계를 만족한다.The molten zinc alloy plated steel material includes 10-30% aluminum (Al), 0.01-0.5% silicon (Si), 0.1-3% magnesium (Mg), and 0.1-0.5% misch metal And the remainder is made of zinc and inevitable impurities. Preferably, the content of aluminum (Al) and silicon (Si) satisfy a relation of 30? Al / Si? 120.
또한 상기 용융 아연합금 도금강재의 도금층은 아연 단상과 아연-알루미늄-마그네슘의 3원 조직이 아연-알루미늄의 2원 공정조직 사이에 존재하는 조직을 갖는다. Further, the plating layer of the hot-dip zinc-plated steel has a structure in which the zinc single phase and the ternary structure of zinc-aluminum-magnesium exist between the binary process structures of zinc-aluminum.
도 1에 나타난 바와 같이, 본 발명인 용융 아연합금 도금강재의 도금층은 Zn-Al 2원 공정조직이 Zn 단상 및 Zn-Mg-Al 3원 조직을 포위하고 있는 형태로 분포되어 있으며, 소지철과 도금층의 계면에 Zn-Fe-Al-Si의 4원계의 두께가 얇은 합금층이 국부적으로 생성된다. 이에 반해, 도 2에 나타난 종래의 아연-알루미늄 도금강재의 도금층은 Zn-Al-Fe의 3원 조직이 도금층의 대부분을 차지하고 있으며, 소지철과 도금층의 계면에 Zn-Fe-Al의 두꺼운 3원계 합금층이 연속적으로 생성된다. As shown in FIG. 1, the plated layer of the hot-dip zinc-plated steel according to the present invention is distributed in a form in which the Zn-Al binary process structure surrounds the Zn single phase and the Zn-Mg-Al three- An alloy layer having a thinner Zn-Fe-Al-Si quaternary system is locally formed at the interface of the interface layer. On the contrary, the conventional zinc-aluminum plated steel plating layer shown in FIG. 2 has a structure in which the ternary structure of Zn-Al-Fe occupies the majority of the plating layer, and the thick three- An alloy layer is continuously produced.
본 발명인 용융 아연합금 도금강재는 도금층이 상기의 조성 및 조직을 만족함으로써, 도금 밀착성 및 절단면 내식성이 우수하고, 균일한 광택도와 조도를 보유하며, 굽힘 가공성이 우수한 용융 아연합금 도금강재를 제공할 수 있다.The hot-dip galvanized steel material of the present invention can provide a hot-dip zinc-alloy-plated steel material excellent in plating adhesion and cut surface corrosion resistance, having uniform luster and roughness, and excellent in bending workability, by satisfying the above composition and structure have.
이하, 실시예를 통하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.
(실시예 1)(Example 1)
탄소 0.025%, 망간 0.2%, 실리콘 0.01% 이하를 함유한 저탄소 열간압연강재(두께 2.3mm)와 냉간압연강재(두께 0.6mm)를 대상으로 전처리 후 하기 표 1의 도금욕 조건에서 용융도금을 실시하였다. Hot-rolled low-carbon hot-rolled steel (thickness: 2.3 mm) and cold-rolled steel (thickness: 0.6 mm) containing 0.025% carbon, 0.2% manganese and 0.01% silicon were subjected to pre- Respectively.
열연강재는 전처리 공정인 산세 처리 후 550℃로 가열처리한 다음, 도금을 실시하였으며, 냉연강재는 탈지 후 750℃에서 소둔한 후 도금을 실시하였다. 이때 환원 분위기는 수소 20%-질소 80%, 이슬점 온도는 -40℃이었다. 도금전 강재의 도 금욕 입욕온도와 도금욕 온도는 각각 510℃∼550℃ 범위에서 합금용용 도금을 실시하였다. The hot - rolled steel was subjected to heat treatment at 550 ℃ after the pickling treatment and then plated. The cold - rolled steel was degreased and annealed at 750 ℃ and then plated. At this time, the reducing atmosphere was hydrogen 20% - nitrogen 80% and the dew point temperature was -40 ° C. Plating bath plating bath temperature and plating bath temperature of the steel before plating were 510 ° C. to 550 ° C., respectively.
상기 합금 용융 도금 후 도금강재의 나내식성, 굽힘밀착성, 표면조도 및 광택도를 측정하여 하기 표 1에 나타내었다. 이때 합금 용융 도금강재의 나내식성은 1,340 시간(2 개월) 염수분무시험 결과 5% 적청 발생시간에 의하여 판단하여 표 1에 나타내었다. 이때 적청 5%이하이면 ◎, 적청 10%이하이면 ○, 적청이 50%이하이면 △, 적청이 50%이상이면 ×로 나타내었다. 하기 표 1에서 발명예와 비교예는 도금욕의 성분 및 도금인자에 의해 결정되므로, 열연강재와 냉연강재를 구별하여 판단하지 않았다.The corrosion resistance, bending adhesion, surface roughness and gloss of the plated steel after the alloy hot-dip coating were measured and are shown in Table 1 below. At this time, the corrosion resistance of the alloy hot-rolled steel was determined by the occurrence time of 5% red rust in the salt spray test of 1,340 hours (2 months), and it is shown in Table 1. In this case, ⊚ indicates that the red color is less than 5%, ∘ indicates that the red color is less than 10%, Δ indicates that the red color is less than 50%, and × when the red color is more than 50%. In the following Table 1, both the hot-rolled steel and the cold-rolled steel were not judged because the inventive and comparative examples were determined by the components of the plating bath and the plating factors.
또한 굽힘 밀착성은 180도 벤딩 후 단면을 관찰하여 크랙 길이가 짧고 크랙 수가 적을수록 양호한 결과로 판단하였다. 이때 크랙이 없으면 ◎, 크랙이 10%이하이면 ○, 크랙이 30%이하이면 △, 크랙이 30%이상이면 ×로 나타내었다. Also, the bending adhesion was evaluated as a good result when the crack length was short and the number of cracks was small by observing the cross section after 180 degrees bending. In this case,? Indicates no crack,? Indicates that the crack is 10% or less,? Indicates that the crack is 30% or less, and? When the crack is 30% or more.
하기 표 1에 나타난 바와 같이, 합금 용융도금 결과 기존의 용융아연도금 강재와 비교하여 나내식성이 훨씬 우수하고 미도금 현상이 관찰되지 않아 도금층 표면 특성이 양호함을 알 수 있었다. 즉 합금도금재의 굽힘 밀착성은 용융아연 도금재와 동등 수준이였으며, 표면 조도와 광택도는 용융아연 도금재와 유사하게 우수하였다.As shown in the following Table 1, as a result of the alloy hot dip galvanizing, the corrosion resistance was much better than that of the conventional hot dip galvanized steel, and no plating phenomenon was observed. That is, the bending adhesion of the alloy plated material was comparable to that of the hot dip galvanized material, and the surface roughness and gloss were similar to those of the hot dip galvanized material.
밀착성flex
Adhesiveness
Corrosion resistance
(Ra,㎛)Surface roughness
(Ra, 占 퐉)
(Gs60o)Glossiness
(Gs60 o )
*MM : La-rich 미슈메탈(Mischmetal)* MM: La-rich Mischmetal
(실시예 2)(Example 2)
탄소 0.005%, 망간 0.10%, 실리콘 0.005% 성분을 함유한 극저탄소강 열간압연강재(두께 1.6mm)와 냉간압연강재(두께 0.4mm)를 대상으로 전처리 후 하기 표 1의 도금욕 조건에서 용융도금을 실시하였다. (1.6 mm in thickness) and cold-rolled steel (0.4 mm in thickness) containing 0.005% of carbon, 0.10% of manganese and 0.005% of silicon were subjected to pretreatment, Respectively.
열연강재는 염산으로 산세 후 550℃에서 열처리 후 도금을 실시하였으며 냉연강재는 탈지 후 820℃에서 열처리하였다. 도금전 강재온도와 도금욕 온도는 각각 510℃∼550℃에서 합금 용용도금을 실시하였다. 이때 환원분위기는 수소 20%-질소 80%, 이슬점 온도 -40℃이었다. 상기와 같이 도금을 행한 후 도금강재의 나내식성, 굽힘가공성, 표면조도 및 광택도를 측정하고 그 결과를 표 2에 나타내었다. 하기 표 2에서 나내식성과 굽힘가공성의 특성평가는 상기 실시예 1의 판단기준에 의하여 나타내었다.The hot rolled steel was pickled with hydrochloric acid and plated after heat treatment at 550 ℃. The cold rolled steel was heat treated at 820 ℃ after degreasing. The temperature of the steel before plating and the temperature of the plating bath were plated for alloy plating at 510 ° C to 550 ° C respectively. At this time, the reducing atmosphere was hydrogen 20% - nitrogen 80% and dew point temperature -40 ° C. After the plating as described above, the corrosion resistance, bending workability, surface roughness and gloss of the plated steel were measured, and the results are shown in Table 2. In Table 2, the evaluation of the corrosion resistance and the bending workability was made according to the criteria of Example 1 above.
하기 표 2에 나타난 바와 같이, 본 발명범위내의 도금욕 조성에서 도금된 용융 도금강재는 기존의 용융아연도금 강재과 비교하여 나내식성이 훨씬 우수하고 미도금 현상이 관찰되지 않아 표면품질이 양호하고 180도 벤딩 후 단면을 관찰한 결과 굽힘 밀착성이 동등 수준이였으며, 표면 조도와 광택도도 양호한 결과를 나타내었다. As shown in the following Table 2, the hot-dip coated steel in the plating bath composition of the present invention had much better corrosion resistance than the conventional hot-dip galvanized steel, and no plating phenomenon was observed, As a result of observing the cross section after bending, the bending adhesion was the same, and the surface roughness and gloss were also good.
밀착성flex
Adhesiveness
(Ra,㎛)Surface roughness
(Ra, 占 퐉)
(Gs60o)Glossiness
(Gs60 o )
*MM : La-rich 미슈메탈(Mischmetal)* MM: La-rich Mischmetal
(실시예 3) (Example 3)
탄소 0.025%, 망간 0.2%, 실리콘 0.01% 이하를 함유한 저탄소강의 열연강재(두께 2.0mm)를 이용하여 표 3의 조건으로 용융 합금도금을 실시하고 굽힘가공성 및 나내식성을 측정하여 그 결과를 표 3에 나타내었다. 하기 표 3에서 나내식성과 굽힘가공성의 특성평가는 상기 실시예 1의 판단기준에 의하여 나타내었다.(Thickness: 2.0 mm) containing 0.025% of carbon, 0.2% of manganese, and 0.01% or less of silicon, and the bending workability and corrosion resistance were measured. Respectively. In Table 3 below, the evaluation of the corrosion resistance and the bending workability was made according to the criteria of Example 1 above.
상기 열연강재는 염산으로 산세 후 도금욕 온도 500∼580℃ 범위에서 도금작업을 행하였고 도금전 강재의 입욕 온도는 475∼550℃ 범위에서 실시하였다. 이때 환원분위기는 수소 20%-질소 80%, 이슬점 온도 -40℃이었다. The hot-rolled steel was pickled with hydrochloric acid and then plated at a plating bath temperature of 500 to 580 ° C, and the bath temperature of the pre-plated steel was 475 to 550 ° C. At this time, the reducing atmosphere was hydrogen 20% - nitrogen 80% and dew point temperature -40 ° C.
하기 표 3에 나타난 바와 같이. 도금욕의 조성과 강재의 도금입욕 온도 및 도금욕의 온도가 본 발명의 범위를 벗어나는 비교예의 경우에는 굽힘가공성 및 나내식성이 우수하지 못하다는 것을 알 수 있다.As shown in Table 3 below. It can be seen that the comparative example in which the composition of the plating bath, the plating bath temperature of the steel material, and the temperature of the plating bath deviate from the range of the present invention, shows that the bending workability and corrosion resistance are not excellent.
온도Plating bath
Temperature
온도Plating bathing
Temperature
밀착성flex
Adhesiveness
*MM : La-rich 미슈메탈(Mischmetal)* MM: La-rich Mischmetal
도 1은 본 발명인 용융 아연합금 도금강재의 도금층을 관찰한 사진이다.1 is a photograph showing a plating layer of a hot-dip galvanized steel material according to the present invention.
도 2는 종래의 아연-알루미늄합금 도금강재의 도금층을 관찰한 사진이다.2 is a photograph showing a plating layer of a conventional zinc-aluminum alloy plated steel material.
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CN104674149A (en) * | 2015-02-27 | 2015-06-03 | 国家电网公司 | Novel steel wire hot-dip galvanizing plating alloy |
KR20190078434A (en) * | 2017-12-26 | 2019-07-04 | 주식회사 포스코 | Zinc alloy coated steel having excellent corrosion resistance after forming, and method for manufacturing the same |
US11566314B2 (en) | 2017-12-26 | 2023-01-31 | Posco Co., Ltd | Zinc alloy plated steel material having excellent corrosion resistance after being processed |
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