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WO2009131267A1 - Composition de placage d'alliage d'aluminium par immersion à chaud et procédé de fabrication d'acier plaqué par alliage d'aluminium par immersion à chaud à l'aide de celle-ci - Google Patents

Composition de placage d'alliage d'aluminium par immersion à chaud et procédé de fabrication d'acier plaqué par alliage d'aluminium par immersion à chaud à l'aide de celle-ci Download PDF

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Publication number
WO2009131267A1
WO2009131267A1 PCT/KR2008/002542 KR2008002542W WO2009131267A1 WO 2009131267 A1 WO2009131267 A1 WO 2009131267A1 KR 2008002542 W KR2008002542 W KR 2008002542W WO 2009131267 A1 WO2009131267 A1 WO 2009131267A1
Authority
WO
WIPO (PCT)
Prior art keywords
hot
aluminum alloy
plating
dip aluminum
plated steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2008/002542
Other languages
English (en)
Inventor
Yong Sug Chung
Jong Min Kim
Jae Min Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DONGBU STEEL Co Ltd
Original Assignee
DONGBU STEEL Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DONGBU STEEL Co Ltd filed Critical DONGBU STEEL Co Ltd
Publication of WO2009131267A1 publication Critical patent/WO2009131267A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C23C2/12—Aluminium or alloys based thereon

Definitions

  • the present invention relates to a hot-dip aluminum alloy plating composition and a method of manufacturing hot-dip aluminum alloy-plated steel using the same, and more particularly, to a hot-dip aluminum alloy plating composition, which makes processability, the corrosion resistance of a shear surface, and the surface gloss of a plating layer superior, and to a method of manufacturing hot-dip aluminum alloy-plated steel using the same.
  • Plated steel having a plating layer composed exclusively of pure aluminum has excellent corrosion resistance in an aqueous solution and in atmosphere, and is therefore utilized as construction material and corrosion- resistant steel material for a piping line.
  • the plated steel having a plating layer composed exclusively of pure aluminum suffers because steel to be plated reacts rapidly with aluminum to thus produce a thick intermetallic compound layer, which functions to drastically deteriorate molding processability . For that reason, the use thereof is very limited.
  • aluminum alloy-plated steel having an alloy layer which is controllably formed with the addition of about 5 ⁇ 11 wt% of Si, has been developed, and is mostly used for heat-resistant parts, such as automobile mufflers, water heaters, heaters, or inner coats of electric rice cookers.
  • the aluminum alloy-plated steel added with Si exhibits superior corrosion resistance for a plain plate while manifesting inferior corrosion resistance for a shear surface and a processed surface, compared to zinc alloy- plated steel.
  • Mg is added so that an [Mg 2 Si] phase is formed in the plating layer, thereby improving corrosion resistance.
  • the addition of Mg is problematic in that the surface hardness of the plating layer is increased and the Mg-based intermetallic compound (Mg 2 Zn, Mg 2 Znii) formed in the plating layer deteriorates the processability of the plated steel.
  • Mg is an element having high affinity for oxygen, an Mg- based oxide film is formed on the surface in the course of wiping and cooling after a plating process. Such a film causes circular surface defects, resulting in reduced surface gloss.
  • the present invention has been made keeping in mind the above problems occurring in the related art, and provides a hot-dip aluminum alloy plating composition, which makes processability, the corrosion resistance of a shear surface, and the surface gloss of a plating layer superior, and also provides a method of manufacturing hot-dip aluminum alloy-plated steel using the same .
  • a hot-dip aluminum alloy plating composition may comprise 5-15 wt% of Si, 3-12 wt% of Mg, and 0.005-0.5 wt% of Sr, with the balance of Al, and may form an Mg 2 Si phase in a plating layer when the surface of steel is plated therewith.
  • a plating structure and an intermetallic compound, in particular, an [Mg 2 Si] phase, formed between a sheet to be plated and an aluminum plating layer may be controlled in terms of size and shape, resulting in hot-dip aluminum alloy-plated steel having improved processability, corrosion resistance of a shear surface, and surface gloss of a plating layer.
  • Si is preferably added in an amount of 5-15 wt%.
  • the amount of Si is less than 5 wt%, effects of adding Si for inhibiting the growth of an alloy layer and improving the flowability of the plating bath to thus impart gloss are not manifested.
  • the amount of Si exceeds 15 wt%, a planar silicon phase is deposited in the plating layer, thus remarkably degrading processability of the plating layer.
  • Mg is an important element for improving corrosion resistance.
  • the Mg component functions to coat the surface of the plating layer and the exposed portion of the steel with an Mg-containing corrosion product so that the inherent corrosion resistance of the hot-dip aluminum alloy-plated steel is further increased.
  • the Mg component in the plating layer forms the [Mg 2 Si] phase as the intermetallic compound along with Si.
  • the [Mg 2 Si] phase is effective for improving the corrosion resistance of the shear surface and the processed portion.
  • Such an intermetallic compound promotes the formation of a stable corrosion product under corrosion conditions, and serves as a supply source of the Mg component. Accordingly, the surface of the plating layer is rapidly coated with a corrosion product, and such a corrosion product acts as a stable protective film, thereby improving the corrosion resistance of the plated surface.
  • Mg exhibits an effect of blocking the diffusion of oxygen via the reaction with aluminum, remarkably improving the corrosion resistance of the shear surface after processing.
  • Mg is present in the form of oxide in the outermost portion of the plating layer, and contributes to an increase in corrosion resistance. Even if the amount thereof is very small, the corrosion resistance effect is large. However, in order to ensure corrosion resistance which is apparently different from in conventional cases, it is preferred that Mg be added in an amount of at least 4.0 wt%. However, in the case where Mg having strong oxidation properties is contained in an excessive amount, the plating bath is saturated and the melting point is increased, thus making it difficult to handle the plating bath. Furthermore, an Mg oxide film is formed on the surface of the plating bath. Therefore, the upper limit of the amount of Mg is preferably set to 12 wt%.
  • the reason why the aluminum alloy plating composition according to the present invention is added with Sr is that the processability of the plating layer is improved, the generation of cracks in the plating layer is prevented, and the surface gloss of the plating layer becomes good.
  • Sr transforming the bulky [Mg 2 Si] phase to be fine, changing the shape thereof, and making the plating structure uniform.
  • the generation of cracks is decreased upon processing, and the propagation of the generated cracks is retarded, generally inhibiting the generation of cracks.
  • the decrease in the generation of cracks is considered to be because the number of directions in which cracks are generated is reduced while the shape of the [Mg 2 Si] phase is changed from a polygon to a quadrangle.
  • the plating structure is transformed to be fine and uniform, thereby reducing the occurrence of circular surface defects on the surface of the plating layer due to the addition of Mg, resulting in greatly increased surface gloss of the plating layer.
  • Such Sr is preferably added in amount of 0.005 ⁇ 0.5 wt%.
  • the amount of Sr is less than 0.005 wt%, the above effects are not manifested.
  • the amount thereof is greater than 0.5 wt%, the outer appearance becomes poor attributable to the adsorption of dross which is regarded as oxide of Sr after a plating process, undesirably resulting in an untidy outer appearance.
  • the adsorption of such dross is shown little by little when the amount of Sr is greater than 0.3 wt%.
  • a method of manufacturing hot-dip aluminum alloy-plated steel may comprise preparing a hot- dip plating bath including 5-15 wt% of Si, 3-12 wt% of Mg, and 0.005-0.5 wt% of Sr, with the balance of Al; immersing steel in the hot-dip plating bath, thus plating the steel; and removing the plated steel from the plating bath and cooling it.
  • Sr is added in an amount greater than 0.3 wt%, the adsorption of dross occurs, and thus, Sr is preferably added in an amount ranging from 0.005 to 0.3 wt%.
  • cooling of the steel may be performed at a rate of 5-30 ° C /sec.
  • the size of the [Mg 2 Si] phase is too large and the processability of the plating layer is deteriorated.
  • cooling is conducted at a rate exceeding 30 ° C /sec, the surface of the plating layer is roughened due to over-cooling, and the [Mg 2 Si] phase is not formed.
  • the cooling rate is the most important factor for adjusting the size and shape of the [Mg 2 Si] phase and is also reguired to increase surface gloss.
  • the cooling rate for increasing the surface gloss is in the range of 10 ⁇ 20 ° C /sec.
  • the hot-dip plating bath preferably has a temperature of 600 ⁇ 700 ° C
  • the temperature of the plating bath is set to 640 ⁇ 660 ° C.
  • the hot-dip aluminum alloy plating composition comprises Si and Mg, and further comprises Sr, thereby realizing a fine [Mg ⁇ Si] phase in the aluminum alloy plating layer, with the changed shape, and making the plating structure uniform.
  • the resulting plated steel can exhibit superior processability, corrosion resistance of a shear surface, and surface gloss.
  • FIG. 1 is an electron micrograph illustrating the side-sectional structure of the plating layer and the alloy layer of the hot-dip aluminum alloy-plated steel according to the present invention
  • FIG. 2 is a graph illustrating the gloss of the hot- dip aluminum alloy-plated steel depending on the added amount of Sr in the case where Sr is added to a plating bath composition of Al - 13wt% Si - 7.5wt% Mg according to the present invention
  • FIG. 3 is electron micrographs illustrating the side- sectional structure of the plating layer and the alloy layer of the hot-dip aluminum alloy-plated steel depending on the added amount of Sr in the case where Sr is added to a plating bath composition of Al - 13wt% Si - 7.5wt% Mg according to the present invention.
  • FIG. 4 is an electron micrograph illustrating the side-sectional structure of the plating layer and the alloy layer of conventional aluminum alloy-plated steel without Sr.
  • a cold rolled steel sheet having a size of 0.7 mm (thickness) x 180 mm (width) x 220 mm (length) was immersed in an alkaline solution at 50 ° C for 30 min, and was then washed with water to remove surface impurities and oil, thus preparing a test sample.
  • a hot-dip plating test was conducted through annealing and plating using a hot-dip plating simulator.
  • the annealing atmosphere was a reducing atmosphere comprising 10 ⁇ 30% hydrogen and 70-90% nitrogen, and the annealing temperature was 750 ⁇ 850 ° C in order to realize necessary mechanical properties.
  • the plating process was conducted by subjecting the sample to cooling so that the temperature thereof was the same as the temperature of the plating bath, immersing the sample in the plating bath for about 3 ⁇ 5 sec, removing the sample therefrom, adjusting the plating amount to about 100 ⁇ 150 g/m 2 (for both surfaces) using an air wiper, and cooling the sample at a rate of 10 ⁇ 20 ° C /sec to solidify it.
  • o indicates ⁇ generation of no defect'
  • * indicates ⁇ generation of one or more defects' .
  • KS D 9502 ASTM B-117
  • the corrosion resistance of a shear surface was evaluated using a 5%/35 ° C NaCl salt spray test method. As such, the upper and lower portions of the shear surface of a test sample were coated, and neither of the side portions thereof was coated. After 1500 hours, the outer appearance was observed with the naked eye, and whether rust was generated was observed with the naked eye.
  • o indicates ⁇ rust generation exceeding 5% but not more than 10%
  • ⁇ indicates ⁇ rust generation exceeding 10% but not more than 30%'
  • x indicates ⁇ rust generation exceeding 30 % ' .
  • a test sample was subjected to a 180° 3T bending test, and the section thereof was observed with the microscope to determine the crack ratio generated per unit length, thus evaluating processability. As such, only cracks across the whole plating layer were observed.
  • o indicates 'crack ratio of 5% or less'
  • ⁇ indicates ⁇ crack ratio exceeding 5% but not more than 12%'
  • x indicates 'crack ratio exceeding 12%' .
  • FIG. 1 is an electron micrograph showing the side- sectional structure of the plating layer and the alloy layer of the hot-dip aluminum alloy-plated steel according to the present invention, specifically, the side-sectional structure of the plating layer and the alloy layer using the plating bath composition of Al - 7.6 wt% Si - 7.3 wt% Mg - 0.5 wt% Sr of Example 1, as shown in Table 1.
  • FIG. 4 shows the side-sectional structure of the plating layer and the alloy layer using the plating bath composition of Al - 6.6 wt% Si - 7.4 wt% Mg of Comparative Example 2, as shown in Table 1. From FIG. 1, it can be seen that, when Sr is added, the bulky [Mg 2 Si] phase is transformed to be fine, and the plating structure is uniform. Further, the surface of the plating layer can be seen to be more even.
  • the plating bath was prepared while adjusting the added amount of Sr. Further, the gloss of the plated steel manufactured using such a plating bath was measured using a gloss meter. The side-section thereof was observed using an electron microscope.
  • FIG. 2 is a graph showing the gloss of the hot-dip aluminum alloy-plated steel depending on the added amount of Sr, when Sr is added to the plating bath composition of Al - 13 wt% Si - 7.5 wt% Mg. As shown in FIG. 2, the gloss was remarkably increased in proportion to the increase in the added amount of Sr.
  • FIG. 3 is electron micrographs showing the side- sectional structure of the plating layer and the alloy layer of the hot-dip aluminum alloy-plated steel depending on the added amount of Sr, when Sr is added to the plating bath composition of Al - 13 wt% Si - 7.5 wt% Mg. From FIG. 3, it can be seen that, when Sr is added, a finely dispersed [Mg 2 Si] phase, which is not bulky, is increased, and the surface of the plating layer is more even than when Sr is not added.
  • the shape of the crystallized [Mg 2 Si] phase is changed from a polygon to a quadrangle.
  • the number of directions in which cracks are generated is decreased, thereby reducing the crack ratio.
  • the change in the shape leads to the formation of the plane of a specific orientation having very high reflectivity on the surface, thereby greatly increasing surface gloss.

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  • 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

L'invention porte sur une composition de placage d'alliage d'aluminium par immersion à chaud et sur un procédé de fabrication d'un acier plaqué par alliage d'aluminium par immersion à chaud utilisant celle-ci. La composition de placage d'alliage d'aluminium par immersion à chaud comprend 5~15 % en poids de Si, 3-12 % en poids de Mg et 0,005-0,5 % en poids de Sr, avec l'équilibre de Al, et forme une phase Mg2Si dans une couche de placage lorsque la surface d'acier est plaquée avec celle-ci. La composition de placage d'alliage d'aluminium par immersion à chaud comprend en outre Sr, en plus de Si et Mg, de telle sorte que la phase [Mg2Si] dans la couche de placage d'alliage d'aluminium devient fine, la forme de celle-ci est changée, et la structure de placage devient uniforme, conduisant à de l'acier plaqué par alliage d'aluminium par immersion à chaud ayant une aptitude supérieure au traitement, une résistance supérieure à la corrosion d'une surface de cisaillement et un brillant de surface supérieur.
PCT/KR2008/002542 2008-04-25 2008-05-06 Composition de placage d'alliage d'aluminium par immersion à chaud et procédé de fabrication d'acier plaqué par alliage d'aluminium par immersion à chaud à l'aide de celle-ci Ceased WO2009131267A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20080038879 2008-04-25
KR10-2008-0038879 2008-04-25

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Publication Number Publication Date
WO2009131267A1 true WO2009131267A1 (fr) 2009-10-29

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PCT/KR2008/002542 Ceased WO2009131267A1 (fr) 2008-04-25 2008-05-06 Composition de placage d'alliage d'aluminium par immersion à chaud et procédé de fabrication d'acier plaqué par alliage d'aluminium par immersion à chaud à l'aide de celle-ci

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CN (1) CN101565806A (fr)
WO (1) WO2009131267A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746422A4 (fr) * 2011-07-14 2015-07-08 Nippon Steel & Sumitomo Metal Corp Tôle d'acier plaquée aluminium présentant un excellent aspect extérieur et une excellente résistance à la corrosion entraînée par un mélange alcool-essence et procédés de fabrication associés
US20160222493A1 (en) * 2013-10-08 2016-08-04 National University Corporation University Of Toyama Casting aluminum alloy and casting produced using the same
EP3088558A4 (fr) * 2013-12-23 2017-01-11 Posco Feuille d'acier pour formation par pressage à chaud ayant une excellente résistance à la corrosion et une excellente soudabilité, élément de formation et son procédé de fabrication

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108796418B (zh) * 2018-06-20 2020-10-20 华冠新型材料股份有限公司 连续热浸镀铝硅镁合金钢板及其制备方法和镀液
CN114807739A (zh) * 2021-01-28 2022-07-29 宝山钢铁股份有限公司 一种镀铝钢板、热成形部件及制造方法
CN117649979B (zh) * 2023-12-04 2024-07-16 西隆电缆有限公司 一种钢芯铝绞线的生产工艺及钢芯铝绞线

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11279734A (ja) * 1998-03-27 1999-10-12 Nisshin Steel Co Ltd 表面性状の優れたＡｌ−Ｓｉ−Ｍｇ系溶融Ａｌ基めっき鋼板
JP2000282204A (ja) * 1999-04-02 2000-10-10 Nippon Steel Corp 端面、加工部の耐食性に優れた建材用アルミめっき鋼板
JP2001073108A (ja) * 1999-06-29 2001-03-21 Nippon Steel Corp 耐食性、外観に優れた溶融アルミめっき鋼板及びその製造法
JP2004083988A (ja) * 2002-08-26 2004-03-18 Nisshin Steel Co Ltd 加工部耐酸化性に優れた耐熱用溶融Ａｌ基めっき鋼板加工材および耐高温酸化被覆構造

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11279734A (ja) * 1998-03-27 1999-10-12 Nisshin Steel Co Ltd 表面性状の優れたＡｌ−Ｓｉ−Ｍｇ系溶融Ａｌ基めっき鋼板
JP2000282204A (ja) * 1999-04-02 2000-10-10 Nippon Steel Corp 端面、加工部の耐食性に優れた建材用アルミめっき鋼板
JP2001073108A (ja) * 1999-06-29 2001-03-21 Nippon Steel Corp 耐食性、外観に優れた溶融アルミめっき鋼板及びその製造法
JP2004083988A (ja) * 2002-08-26 2004-03-18 Nisshin Steel Co Ltd 加工部耐酸化性に優れた耐熱用溶融Ａｌ基めっき鋼板加工材および耐高温酸化被覆構造

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2746422A4 (fr) * 2011-07-14 2015-07-08 Nippon Steel & Sumitomo Metal Corp Tôle d'acier plaquée aluminium présentant un excellent aspect extérieur et une excellente résistance à la corrosion entraînée par un mélange alcool-essence et procédés de fabrication associés
US20160222493A1 (en) * 2013-10-08 2016-08-04 National University Corporation University Of Toyama Casting aluminum alloy and casting produced using the same
US10023943B2 (en) * 2013-10-08 2018-07-17 National University Corporation University Of Toyama Casting aluminum alloy and casting produced using the same
EP3088558A4 (fr) * 2013-12-23 2017-01-11 Posco Feuille d'acier pour formation par pressage à chaud ayant une excellente résistance à la corrosion et une excellente soudabilité, élément de formation et son procédé de fabrication
US10570493B2 (en) 2013-12-23 2020-02-25 Posco Steel sheet for hot press forming with excellent corrosion resistance and weldability, forming member, and manufacturing method therefor

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