US20140017516A1 - Hot dipped galvanized steel sheet with excellent deep drawing properties and ultra-low temperature adhesive brittleness, and preparation method thereof - Google Patents

Hot dipped galvanized steel sheet with excellent deep drawing properties and ultra-low temperature adhesive brittleness, and preparation method thereof Download PDF

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Publication number
US20140017516A1
US20140017516A1 US13/980,595 US201113980595A US2014017516A1 US 20140017516 A1 US20140017516 A1 US 20140017516A1 US 201113980595 A US201113980595 A US 201113980595A US 2014017516 A1 US2014017516 A1 US 2014017516A1
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steel sheet
hot
galvanized steel
dipped galvanized
plating layer
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US13/980,595
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Inventor
Seung-Bok Lee
Jun-Woo Park
Hyun-Jun Tark
Moon-Hi Hong
Ju-Youn Lee
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Posco Holdings Inc
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Posco Co Ltd
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Assigned to POSCO reassignment POSCO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEE, JU-YOUN, LEE, SEUNG-BOK, TARK, Hyun-Jun, HONG, Moon-Hi, PARK, JUN-WOO
Publication of US20140017516A1 publication Critical patent/US20140017516A1/en
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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
    • C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • 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
    • 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
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]

Definitions

  • the present invention relates to a hot-dipped galvanized steel sheet, and more particularly, to a hot-dipped galvanized steel sheet having improved deep drawing properties and low-temperature adhesive brittleness, and a method of manufacturing the hot-dipped galvanized steel sheet.
  • steel sheets are galvanized by passing a steel sheet through molten zinc contained in a bath and solidifying the molten zinc applied to the steel sheet.
  • molten zinc applied to a steel sheet solidifies, coarse dendritic crystal grains, called spangles, are formed on the surface of the molten zinc. Generation of such spangles is a characteristic of zinc solidification.
  • spangles are generated.
  • the size of spangles may be determined by the basic structure of the zinc plating layer formed in an initial stage of plating.
  • spangles decrease the adhesive strength of paint on a zinc plating layer and the corrosion resistance of a steel sheet, and even though a zinc plating layer is painted, spangles still make the surface of the zinc plating layer uneven and spoils the appearance of a zinc-plated steel sheet because spangles can be seen through paint.
  • an inorganic salt solution may be sprayed on a steel sheet before molten zinc applied to the steel sheet is solidified, so as to minimize the size of spangles formed on the steel sheet.
  • the inorganic salt solution is sprayed on the steel sheet through an electrode disposed on the front side of a nozzle. Since the inorganic salt solution is sprayed through the electrode, droplets of the inorganic salt solution are charged with static electricity and are thus easily attached to the steel sheet by electrical attraction to minify the metallographic structure of a zinc plating layer.
  • a phosphate solution is widely used as the inorganic salt solution.
  • a plating layer having spangles of 150 ⁇ m or less can be formed on a steel sheet by spraying droplets of a phosphate solution charged with electricity as described above.
  • the steel sheet can have a aesthetically-pleasing appearance, improved image clarity after painting, and high corrosion resistance, and the plating layer can be prevented from breaking into flaking during a press process.
  • spangles are formed to have different shapes depending on how hexagonal crystals of zinc are formed on the surface of a steel sheet. In other words, since hexagonal crystals of zinc grow in different angles in different regions of a steel sheet, spangles have different shapes.
  • FIG. 1A illustrates a hot-dipped galvanized steel sheet on which spangles having a size of 150 ⁇ m or less are formed
  • FIG. 1B illustrates a hot-dipped galvanized steel sheet on which spangles having a size of 400 ⁇ m or greater are formed.
  • relatively large zinc crystals are randomly oriented, advantageous in terms of brittleness but disadvantageous in terms of the appearance of the steel sheet.
  • the spangles have the same crystallographic orientation in a manner such that the basal planes of zinc, (0001) planes, are parallel to the surface of the steel sheet.
  • the above-mentioned crystallographic orientation of zinc in which the basal planes of zinc crystals are parallel to the surface of the steel sheet is known to be most effective in preventing corrosion, a black patina, and chemical instability. Until recently, there have been many efforts to improve such properties.
  • Japanese Patent Application Laid-open Publication No.: 1999-100653 discloses a technique for adjusting the size of spangles to be within 60 ⁇ m to 1000 ⁇ m by spraying mist through a nozzle
  • Japanese Patent Application Laid-open Publication No.: 1996-188863 discloses a technique for adjusting the size of spangles to be 50 ⁇ m or less and the level of surface roughness to be within 0.4 ⁇ m to 1.0 ⁇ m.
  • U.S. Pat. No. 4,500,561 discloses a technique for decreasing the size of spangles to 1000 ⁇ m or less by using droplets passed through an electric field.
  • structural adhesives are used after determining whether plated steel sheets can be joined using the structural adhesives at a low temperature of ⁇ 40° C. for the case of using automobiles in polar regions.
  • an adhesive is used for a galvanized steel sheet in which the (0001) planes of zinc crystals are parallel to the surface of the steel sheet and thus spangles are not formed, a zinc plating layer may easily be stripped from the steel sheet at a low temperature of ⁇ 40° C. or during a deep drawing process.
  • the brittleness of a zinc plating layer increases if spangles of the zinc plating layer are small, and the (0001) planes (basal planes) of the zinc plating layer function as slip planes or cleavage planes. Therefore, if a zinc plating layer formed on a steel sheet has small spangles or the (0001) planes of zinc crystals of the zinc plating layer are parallel to the surface of the steel sheet, the zinc plating layer may easily be stripped from the steel sheet when the steel sheet is impacted.
  • aspects of the present invention provide a hot-dipped galvanized steel sheet having improved deep drawing properties and low-temperature adhesive brittleness by controlling the structure and grain size of a zinc plating layer, and a method of manufacturing the hot-dipped galvanized steel sheet.
  • a hot-dipped galvanized steel sheet with improved deep drawing properties and low-temperature adhesive brittleness including a zinc plating layer, wherein grains of the zinc plating layer have an average particle diameter of 150 ⁇ m to 400 ⁇ m, and intensity of preferred orientation of (0001) planes of the zinc plating layer is from 3000 cps (count per second) to 20000 cps.
  • a method of manufacturing a hot-dipped galvanized steel sheet including: applying molten zinc to a steel sheet; adjusting the amount of the molten zinc applied to the steel sheet; spraying an aqueous solution on the steel sheet; cooling the steel sheet; and performing a skin pass milling process on the steel sheet, wherein the spraying of the aqueous solution includes spraying electrically charged demi-water (demineralized water) on the steel sheet.
  • demi-water demineralized water
  • the hot-dipped galvanized steel sheet can have a reduced size deviation, the intensity of orientation of the (0001) planes of zinc crystals of the zinc plating layer can be lowered, and the volume fraction of crystallographic twins of the zinc plating layer can be increased. Therefore, the hot-dipped galvanized steel sheet can have improved properties such as deep drawing properties, bending properties, and adhesive brittleness.
  • FIG. 1A is a schematic view illustrating the crystallographic structure of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 150 ⁇ m or less are formed
  • FIG. 1B is a schematic view illustrating the crystallographic structure of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 400 ⁇ m or greater are formed.
  • FIG. 2A is an X-ray analysis graph illustrating the crystallographic orientation of (0001) planes of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 150 ⁇ m or less are formed
  • FIG. 2B is an X-ray analysis graph illustrating the crystallographic orientation of (0001) planes of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 400 ⁇ m or greater are formed.
  • FIGS. 3A and 3B are images illustrating evaluation results of low-temperature adhesive brittleness of Comparative Samples 1 and Inventive Samples 1.
  • crystal grains of a zinc plating layer of a hot-dipped galvanized steel sheet have an average particle diameter of 150 ⁇ m to 400 ⁇ m.
  • the hot-dipped galvanized steel sheet may have a beautiful appearance owing to small spangles but the zinc plating layer may have unsatisfactory low-temperature adhesive brittleness.
  • the average particle diameter of the crystal grains is greater than 400 ⁇ m, even though the zinc plating layer may have satisfactory low-temperature adhesive brittleness, the hot-dipped galvanized steel sheet may have a poor appearance and image clarity, and the zinc plating layer may easily be separated from the hot-dipped galvanized steel sheet during a continuous press process due to coarse spangles.
  • the crystal grains of the zinc plating layer of the hot-dipped galvanized steel sheet have a minimum diameter of 30 ⁇ m and the deviation of the diameters of the crystal grains be 40% or less of the average particle diameter of the crystal grains.
  • the zinc plating layer includes crystal grains having a diameter of 30 ⁇ m or less, the crystal grains may be more brittle than surrounding crystal grains, and thus cracks may start from the crystal grains.
  • the zinc plating layer may be separated from the hot-dipped galvanized steel sheet, and thus the formability of the hot-dipped galvanized steel sheet may be deteriorated.
  • the deviation of the diameters of the crystal grains of the zinc plating layer be 40% or less of the average particle diameter of the crystal grains. That is, it may be preferable that the size of spangles formed on the zinc plating layer be uniform within that range. If the deviation is greater than 40% and thus the size of zinc crystals is not uniform, when the hot-dipped galvanized steel sheet undergoes plastic deformation, the zinc plating layer may receive non-uniformly applied force and may thus be partially separated from the hot-dipped galvanized steel sheet. Therefore, to prevent problems related to adhesive brittleness, it may be preferable that the deviation of the diameters of crystal grains be 40% or less of the average particle diameter of the crystal grains.
  • the intensity of preferred orientation of the (0001) planes of the zinc plating layer of the hot-dipped galvanized steel sheet be from 3000 cps to 20000 cps (count per second).
  • the intensity of preferred orientation of the zinc plating layer of the hot-dipped galvanized steel sheet was measured to be from 3000 cps to 20000 cps.
  • the maximum intensity of the (0001) planes of zinc crystals was measured to be from 3000 cps to 20000 cps (the tilt angle of a sample was 5°, and intensity values measured at intervals of 5° in a rotational angle of 0° to 360° were averaged).
  • the intensity of preferred orientation of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 150 ⁇ m or less are formed is greater than 20,000 cps
  • the intensity of preferred orientation of a hot-dipped galvanized steel sheet of the related art on which spangles having a size of 400 ⁇ m or greater is formed on is less than 3000 cps.
  • the intensity of preferred orientation of (0001) planes is adjusted to be within the range of 3000 cps to 20000 cps. If the intensity of preferred orientation of (0001) planes is less than 3000 cps, it is advantageous in terms of the brittleness of a zinc plating layer but disadvantageous in terms of appearance due to coarse spangles. On the other hand, if the intensity of preferred orientation of (0001) planes is greater than 20000 cps, the appearance of a zinc plating layer may be good, owing to small spangles but the deep drawing properties and low-temperature brittleness of the zinc plating layer may be deteriorated.
  • the volume fraction of crystallographic twins of the zinc plating layer of the hot-dipped galvanized steel sheet may be 30% or greater.
  • Crystallographic twins may be present in the zinc plating layer when the hot-dipped galvanized steel sheet is processed through a skin pass milling process, and in zinc crystals having a hexagonal close-packed (HCP) structure, crystallographic twins function as an important plastic deformation mechanism to facilitate a deep drawing process and improve brittleness characteristics.
  • HCP hexagonal close-packed
  • volume fraction of crystallographic twins of the zinc plating layer is less than 30%, plastic deformation may be less facilitated, and the workability of the hot-dipped galvanized steel sheet may be deteriorated particularly when the size of the zinc crystals of the zinc plating layer is from 150 ⁇ m to 400 ⁇ m.
  • a method of manufacturing a hot-dipped galvanized steel sheet includes: applying molten zinc to a steel sheet; adjusting the amount of the molten zinc applied to the steel sheet; spraying an aqueous solution on the steel sheet; cooling the steel sheet; and performing a skin pass milling process on the steel sheet.
  • the spraying of the aqueous solution is performed by spraying electrically charged demi-water (demineralized water) on the steel sheet.
  • the applying of the molten zinc is performed by passing the steel sheet through a zinc plating solution to attach molten zinc to the steel sheet.
  • the applying of the molten zinc is not limited to a particular method or process. That is, molten zinc may be applied to the steel sheet using any zinc plating solution and process conditions that are commonly used for manufacturing hot-dipped galvanized steel sheets in the art to which the present invention pertains.
  • the zinc plating solution may include aluminum (Al), antimony (Sb), and/or lead (Pb).
  • the steel sheet may be any kind of steel sheet. That is, any steel sheet used for manufacturing a hot-dipped galvanized steel sheet in the related art may be used.
  • the steel sheet is air-wiped to remove an excessive amount of the zinc plating solution from the steel sheet.
  • the amount of the molten zinc applied to the steel sheet may be adjusted to be any degree considered appropriate by those of skill in the art to which the present invention pertains. That is, the amount of the molten zinc applied to the steel sheet is not limited to any particular degree. For example, the amount of the molten zinc applied to the steel sheet may be adjusted according to the purpose of the steel sheet.
  • the spraying of the aqueous solution is performed by spraying electrically charged demi-water on the steel sheet to solidify the molten zinc.
  • the electrically charged demi-water is sprayed so as to form a uniform zinc plating layer having uniformly sized spangles. If a solution is electrically charged and sprayed in the form of mist, droplets of the solution collide with a molten zinc plating layer and absorb heat from the molten zinc plating layer to facilitate solidification of the molten zinc plating layer.
  • regions of the molten zinc plating layer colliding with nuclear particles such as phosphate nuclear particles may lose heat much more quickly than other regions.
  • relatively small spangles may be formed on the regions, and relatively large spangles may be formed on the other regions to increase the deviation of the sizes of the spangles.
  • the zinc plating layer of the hot-dipped galvanized steel sheet may not be uniformly stressed during a deep drawing process, and thus cracks may start from relatively small spangles.
  • the zinc plating layer may be separated from the hot-dipped galvanized steel sheet. That is, a large deviation of the sizes of spangles may deteriorate the formability of the hot-dipped galvanized steel sheet.
  • demi-water injection pressure of 0.3 kgf/cm 2 to 5.0 kgf/cm 2
  • an air injection pressure of 0.5 kgf/cm 2 to 7.0 kgf/cm 2
  • demi-water pressure/air pressure ratio of 1/10 to 8/10.
  • the demi-water is sprayed at a pressure of lower than 0.3 kgf/cm 2 , spangles may not be minified. If the demi-water is sprayed at a pressure of greater than 5.0 kgf/cm 2 , pitting marks may be formed on the steel sheet while the steel sheet collide with droplets of the demi-water, and thus the appearance of the steel sheet may be spoiled.
  • the front side of the nozzle may be charged to have a voltage of ⁇ 1 KV to ⁇ 25 KV. If the front side of the nozzle is charged to have a voltage of less than ⁇ 1 KV, electrical attraction may not be sufficient to minify droplets and spangles. On the other hand, if the front side of the nozzle is charged to a voltage of greater than ⁇ 25 KV, spangles smaller than 150 pm may be formed on the zinc plating layer, and thus deep drawing properties and adhesive brittleness may be deteriorated.
  • a skin pass milling process is performed on the steel sheet.
  • crystallographic twins are formed in the zinc plating layer.
  • the skin pass milling process may be performed at an elongation of 5% or less.
  • the skin pass milling process be performed at an elongation of 5% or less.
  • crystallographic twins are formed, which function as an important processing mechanism in zinc crystals having an HCP structure because the HCP structure has few deformation mechanisms.
  • the intensity of preferred orientation of the (0001) planes of zinc crystals may be lowered.
  • the skin pass milling process is not performed, the bonding between the zinc plating layer and the steel sheet may not be firm, and the formability of the steel sheet may not be good.
  • the skin pass milling process is performed at an elongation of greater than 5%, the properties of the steel sheet may be deteriorated even though the formability and adhesiveness of the zinc plating layer are improved.
  • Hot-dipped galvanized steel sheets were treated with a phosphate solution or demi-water under the conditions shown in Table 1 to adjust the size of spangles. Thereafter, the steel sheets were treated through a skin pass milling process at an elongation of 1.0% and a roll pressure of 200 tons to 240 tons, and the adhesive brittleness, appearance, and image clarity of the hot-dipped galvanized steel sheets were measured as shown in Table 1.
  • the hot-dipped galvanized steel sheets were prepared by performing a hot-dip galvanization process on soft IF steel sheets having a thickness of 0.67 mm to form zinc plating layers on the steel sheets at a plating density of 70 g/m 2 .
  • Sizes and size deviations of spangles formed on the zinc plating layers were measured and analyzed using an optical microscope and an image analyzer before the hot-dipped galvanized steel sheets were treated through the skin pass milling process.
  • the measured and analyzed results are shown in the “spangle size” and “spangle size deviation” columns of Table 1 below.
  • Adhesive brittleness was measured by bonding two hot-dipped galvanized steel sheets with an adhesive for automotive structural parts (Sealer Terokal 5089 by Henkel Korea, Ltd.), keeping the bonded hot-dipped galvanized steel sheets at ⁇ 40° C., impacting the hot-dipped galvanized steel sheets with a wedge, and observing separation of zinc plating layers of the hot-dipped galvanized steel sheets.
  • O denotes the case where a zinc plating layer was not stripped off
  • ⁇ denotes the case where 20% or less of a zinc plating layer was stripped off
  • X denotes the case where 50% or more of a zinc plating layer was stripped off. Appearance and image clarity were measured with the naked eye, and results thereof are denoted as good (O), fair ( ⁇ ), and poor (X) in Table 1.
  • Inventive Samples treated with demi-water have spangles within a preferable size range, intensity of preferred orientation within the range of 3000 cps to 20000 cps, size deviations within a preferable range, good adhesive brittleness, and good appearance.
  • Comparative Sample 1 treated with demi-water has spangles within a preferable size range, Comparative Sample 1 has an unacceptably large spangle size deviation, an unacceptably high degree of intensity of preferred orientation, and poor adhesive brittleness.
  • Comparative Samples 2 to 5 treated with a phosphate solution have unsatisfactory adhesive brittleness or appearance.
  • Comparative Sample 6 a general hot-dipped galvanized steel sheet has poor appearance.
  • FIGS. 3A and 3B are images for evaluating adhesive brittleness of Comparative Samples 1 and Inventive Samples 1. Adhesive brittleness was evaluated based on whether a blue adhesive remained. Referring to Comparative Samples 1 shown in FIG. 3A , as indicated by circles, an adhesive does not remain after zinc plating layers are fractured. Referring to Inventive Samples 1 shown in FIG. 3B , an adhesive remains owing to improved adhesive brittleness.

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US13/980,595 2011-01-20 2011-01-20 Hot dipped galvanized steel sheet with excellent deep drawing properties and ultra-low temperature adhesive brittleness, and preparation method thereof Abandoned US20140017516A1 (en)

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US11078564B2 (en) * 2015-12-22 2021-08-03 Posco Hot-dip galvanized steel sheet with excellent surface quality and resistance to low temperature brittle fracture
US11801665B2 (en) 2018-11-29 2023-10-31 Posco Co., Ltd Hot-dip galvanized steel sheet having excellent surface appearance and low-temperature bonding brittleness

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CN108350555A (zh) * 2015-10-26 2018-07-31 Posco公司 弯曲加工性优异的镀锌合金钢板及其制造方法
CN106702101B (zh) * 2016-08-30 2018-09-14 重庆万达薄板有限公司 连续热镀有花镀锌钢板的制备工艺
WO2024019059A1 (ja) * 2022-07-19 2024-01-25 国立大学法人大阪大学 無機構造体及び無機構造体の製造方法

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WO2012099284A1 (ko) 2012-07-26
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JP5816703B2 (ja) 2015-11-18
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