WO2023238934A1 - Ｚｎ－Ａｌ－Ｍｇ系溶融めっき鋼板 - Google Patents

Ｚｎ－Ａｌ－Ｍｇ系溶融めっき鋼板 Download PDF

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Publication number
WO2023238934A1
WO2023238934A1 PCT/JP2023/021552 JP2023021552W WO2023238934A1 WO 2023238934 A1 WO2023238934 A1 WO 2023238934A1 JP 2023021552 W JP2023021552 W JP 2023021552W WO 2023238934 A1 WO2023238934 A1 WO 2023238934A1
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Prior art keywords
hot
phase
dip
plating layer
mass
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PCT/JP2023/021552
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English (en)
French (fr)
Japanese (ja)
Inventor
哲也 鳥羽
保明 河村
勇亮 小東
智仁 田中
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Nippon Steel Corp
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Nippon Steel Corp
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Priority to EP23819914.5A priority Critical patent/EP4538410A4/en
Priority to US18/872,647 priority patent/US20250369082A1/en
Priority to JP2024527033A priority patent/JPWO2023238934A1/ja
Priority to KR1020247040945A priority patent/KR20250010042A/ko
Priority to CN202380044360.9A priority patent/CN119301292A/zh
Priority to AU2023282694A priority patent/AU2023282694A1/en
Publication of WO2023238934A1 publication Critical patent/WO2023238934A1/ja
Priority to MX2024014723A priority patent/MX2024014723A/es
Anticipated expiration legal-status Critical
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
    • 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
    • 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
    • C23C2/026—Deposition of sublayers, e.g. adhesion layers or pre-applied alloying elements or corrosion protection
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process

Definitions

  • the present invention relates to a Zn-Al-Mg hot-dip galvanized steel sheet with a glossy appearance.
  • Hot-dip galvanized steel sheets are used as steel sheets with good corrosion resistance.
  • Hot-dip galvanized steel sheets which are a typical example of hot-dip galvanized steel sheets, are widely used in various manufacturing industries such as automobiles, home appliances, and building materials. Further, for the purpose of further improving the corrosion resistance of hot-dip galvanized steel sheets, highly corrosion-resistant hot-dip galvanized steel sheets have been proposed in which the hot-dip galvanized layer contains Al or Mg.
  • Patent Documents 1 to 3 propose Zn-Al-Mg hot-dip galvanized steel sheets.
  • Zn-Al-Mg hot-dip coated steel sheets have [Al phase], [Zn phase], [MgZn two phases], [ternary eutectic structure of Al/MgZn 2 /Zn], Mainly includes four types of phases and structures.
  • Si is contained in the hot-dip plating layer in addition to Zn, Al, and Mg, in addition to the above four types of phases and structures, there are mainly five types of phases and structures including [Mg 2 Si phase].
  • the hot-dip coating layer of the Zn-Al-Mg hot-dip galvanized steel sheet contains various phases and structures, so the surface of the hot-dip coating layer has a satin-like appearance.
  • Zn-Al-Mg hot-dip coated steel sheets are widely used in various manufacturing industries such as automobiles, home appliances, and building materials.
  • customer demands for the surface appearance of plated steel sheets have been increasing, and Zn--Al--Mg hot-dip coated steel sheets are required to have an appearance with stronger metallic luster.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a Zn-Al-Mg-based hot-dip plated steel sheet that has superior metallic luster on the surface of a hot-dip plated layer and excellent corrosion resistance compared to conventional ones.
  • the present invention employs the following configuration.
  • the hot-dip plating layer has an average composition of more than 10 to 22% by mass of Al, 1.0 to 10% by mass of Mg, and the remainder contains Zn and impurities,
  • the thickness of the hot-dip plating layer is t, and a 5 mm square cross section parallel to the surface of the hot-dip plating layer is exposed at any position of 3t/4 position, t/2 position, or t/4 position from the surface of the hot-dip plating layer.
  • a Zn-Al-Mg hot-dipped steel sheet wherein the area fraction of the [Zn phase] in the plating structure in at least one cross section is less than 20%.
  • the hot-dip plating layer has an average composition of more than 10 to 22% by mass of Al, 1.0 to 10% by mass of Mg, and the remainder contains Zn and impurities, Furthermore, it contains one or two selected from the group consisting of Group A and Group B below,
  • the thickness of the hot-dip plating layer is t, and a 5 mm square cross section parallel to the surface of the hot-dip plating layer is exposed at any position of 3t/4 position, t/2 position, or t/4 position from the surface of the hot-dip plating layer.
  • a Zn-Al-Mg hot-dipped steel sheet wherein the area fraction of the [Zn phase] in the plating structure in at least one cross section is less than 20%.
  • Si 0.0001 to 2% by mass
  • Group B Any one or two of Ni, Ti, Zr, Sr, Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, Hf, and C 0.0001 to 2% by mass of seeds or more in total
  • the ratio of the area fraction B of [Zn phase] to the total area fraction A of [Zn phase] and [ternary eutectic structure of Al/MgZn 2 /Zn] of the plating structure in at least one cross section The Zn-Al-Mg hot-dipped steel sheet according to [1] or [2], wherein B/A (%)) is less than 20%.
  • FIG. 1 is a schematic cross-sectional view illustrating an exposed surface for measuring the plating structure of a hot-dip coating layer in a Zn-Al-Mg hot-dip galvanized steel sheet according to an embodiment of the present invention.
  • FIG. 2 is a perspective view illustrating an exposed surface for measuring the plating structure of a hot-dip coating layer in a Zn-Al-Mg hot-dip galvanized steel sheet according to an embodiment of the present invention.
  • the present inventors investigated in detail the plating layer of a conventional Zn-Al-Mg hot-dip plated steel sheet that exhibits a satin-like appearance.
  • the satin-like appearance is caused by the coexistence of fine shiny parts exhibiting metallic luster and fine white parts exhibiting white color.
  • the area fraction of the [Zn phase] on the surface of the plating layer was smaller than that in the white part.
  • the ratio of the [Zn phase] to the [ternary eutectic structure of Al/MgZn 2 /Zn] was higher than that in the glossy part.
  • the present inventors conducted extensive studies to obtain a glossy appearance as a whole by increasing the number of glossy parts and reducing the white parts in the hot-dip plating layer, and found that while adjusting the chemical components of the hot-dip plating layer, It has been found that by reducing the proportion of [Zn phase], the surface appearance of the plating layer as a whole comes to exhibit metallic luster. In addition, by lowering the ratio of the [Zn phase] to the total of [ternary eutectic structure of Al/MgZn 2 /Zn] and [Zn phase] in the entire plating layer, the appearance of the plating layer has a more metallic luster. We found that
  • the Zn-Al-Mg hot-dip plated steel sheet of the present embodiment includes a steel plate and a hot-dip coating layer formed on the surface of the steel plate, and the average composition of the hot-dip coating layer is Al: more than 10 to 22% by mass. , Mg: 1.0 to 10% by mass, and the remainder contains Zn and impurities, and the thickness of the hot-dip plating layer is t, and the position is 3t/4 position, t/2 position, or t/2 position from the surface of the hot-dip plating layer.
  • the area fraction of the [Zn phase] in the plating structure in at least one cross section is less than 20%.
  • the 5 mm square cross section parallel to the surface of the plating layer refers to a square exposed surface that is parallel to the surface and has a width of 5 mm square in plan view.
  • the steel material that forms the base of the hot-dip plating layer there are no particular restrictions on the steel material that forms the base of the hot-dip plating layer.
  • the material it can be applied to general steel, Al-killed steel, and some high-alloy steels, and there are no particular restrictions on the shape. Further, the steel material may be subjected to Ni pre-plating.
  • the hot-dip plating layer according to this embodiment is formed by applying the hot-dip plating method described below to the steel material.
  • the hot-dip plating layer according to the present embodiment contains, on average, more than 10 to 22% by mass of Al, 1.0 to 10% by mass of Mg, and the remainder includes Zn and impurities. Furthermore, it may contain one or two selected from the group consisting of Group A and Group B below. [Group A] Si: 0.0001 to 2% by mass [Group B] Any one or two of Ni, Ti, Zr, Sr, Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, Hf, and C 0.0001 to 2% by mass of seeds or more in total
  • the content of Al is in the range of more than 10% by mass and 22% by mass or less in terms of average composition.
  • Al is an element necessary to ensure corrosion resistance. If the content of Al in the hot-dip coating layer is 10% by mass or less, the effect of improving corrosion resistance becomes insufficient, and if it exceeds 22% by mass, the corrosion resistance decreases, although the cause is unknown. From the viewpoint of corrosion resistance, the content is preferably more than 10% by mass and 20% by mass or less. More preferably, it is more than 10% by mass and 18% by mass or less. More preferably, it is 11% by mass or more. Moreover, it is more preferably 19% by mass or less.
  • the Mg content is in the range of 1.0 to 10% by mass in terms of average composition.
  • Mg is an element necessary to improve the corrosion resistance of the hot-dip plated layer. If the content of Mg in the hot-dip coating layer is less than 1.0% by mass, the effect of improving corrosion resistance will be insufficient, and if it exceeds 10% by mass, dross generation in the plating bath will become significant, and it will not be possible to coat steel materials stably. It becomes difficult to manufacture.
  • the content is preferably 1.5% by mass or more. Moreover, it is preferably 8% by mass or less. More preferably, it is 2% by mass or more. Further, it is more preferably 6% by mass or less.
  • the hot-dip plating layer may contain Si in a range of 0.0001 to 2% by mass.
  • Si is an effective element for improving the adhesion of the hot-dip plating layer. It is preferable to contain Si in an amount of 0.0001% by mass or more because the effect of improving adhesion is exhibited by containing 0.0001% by mass or more of Si.
  • the effect of improving plating adhesion is saturated even if the content exceeds 2% by mass, so the content of Si is set to 2% by mass or less.
  • the content may be 0.01% by mass or more, or may be 1% by mass or less. Furthermore, it may be set to 0.03% by mass or more, or may be set to 0.8% by mass or more.
  • the average composition of the hot-dip plating layer is Ni, Ti, Zr, Sr, Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, Hf. , C may be contained in a total amount of 0.0001 to 2% by mass. Further, the content may be in the range of 0.01 to 2% by mass. By containing these elements, corrosion resistance can be further improved.
  • REM is one or more rare earth elements with atomic numbers 57 to 71 in the periodic table.
  • the remainder of the chemical components of the hot-dip plated layer are zinc and impurities.
  • composition of the hot-dip plating layer can be measured by the following method. First, the surface coating film is removed with a paint film remover that does not corrode the plating (for example, Neoliver SP-751 manufactured by Sansai Kako Co., Ltd.), and then the hot-dip plating layer is removed with hydrochloric acid containing an inhibitor (for example, Hibiron manufactured by Sugimura Kagaku Kogyo Co., Ltd.). It can be determined by dissolving and subjecting the resulting solution to inductively coupled plasma (ICP) emission spectroscopic analysis.
  • ICP inductively coupled plasma
  • the structure of the hot-dip plating layer of this embodiment may have the following structure, for example.
  • the hot-dip plating layer containing Al, Mg, and Zn includes [Al phase], [MgZn 2 phase], [Zn phase], and [ternary eutectic structure of Al/Zn/MgZn 2] . Specifically, it has a form in which [Al phase], [MgZn 2 phase], and [Zn phase] are included in the matrix of [ternary eutectic structure of Al/Zn/MgZn 2 ]. Moreover, when Si is contained, [Mg 2 Si phase] may be included in the matrix of [ternary eutectic structure of Al/Zn/MgZn 2 ].
  • [Ternary eutectic structure of Al/Zn/MgZn 2 ] is a ternary eutectic structure of an Al phase, a Zn phase, and an intermetallic compound MgZn 2 phase, and this ternary eutectic structure is formed.
  • the Al phase corresponds to, for example, the "Al'' phase (which is an Al solid solution containing Zn and contains a small amount of Mg) at high temperature in the ternary equilibrium phase diagram of Al-Zn-Mg.
  • the Zn phase in the ternary eutectic structure contains a small amount of Al as a solid solution, and in some cases is a Zn solid solution containing a small amount of Mg.
  • the MgZn two phase in the ternary eutectic structure is a metal that exists near Zn: about 84% by mass in the Zn-Mg binary equilibrium phase diagram. It is an intermediate compound phase. As far as we can see from the phase diagram, it is thought that other additive elements are not solidly dissolved in each phase, or even if they are solidly dissolved, the amount is extremely small. However, since the amounts cannot be clearly distinguished by ordinary analysis, the ternary eutectic structure consisting of these three phases is herein referred to as [ternary eutectic structure of Al/Zn/MgZn 2 ].
  • Al phase is a phase that appears like an island with clear boundaries in the matrix of [ternary eutectic structure of Al/Zn/MgZn2 ] , and this is due to the ternary system equilibrium of Al-Zn-Mg, for example.
  • the amount of dissolved Zn and Mg in this Al'' phase at high temperature differs depending on the Al and Mg concentrations in the plating bath.
  • the Al'' phase at high temperature is normally different from the fine Al phase at room temperature.
  • the island-like shape seen at room temperature is thought to be due to the shape of the Al'' phase at high temperatures.
  • the phase that is derived from the Al'' phase at high temperatures and whose shape is due to the shape of the Al'' phase is herein referred to as the [Al phase].
  • [Al phase] can be clearly distinguished from the Al phase forming [ternary eutectic structure of Al/Zn/MgZn 2] by microscopic observation.
  • [Zn phase] is a phase that appears like an island with clear boundaries in the matrix of [ternary eutectic structure of Al/Zn/MgZn2 ] , and actually contains a small amount of Al or Mg in solid solution. There's something I'm doing. As far as we can see from the phase diagram, it is thought that this phase does not contain any other additive elements, or even if they do, the amount is extremely small.
  • [Zn phase] is a region where the Zn phase has an equivalent circle diameter of 2.5 ⁇ m or more, and it is clearly distinguished from the Zn phase forming [ternary eutectic structure of Al/Zn/MgZn 2] by microscopic observation. can be distinguished into
  • [MgZn 2- phase] [MgZn 2 phase] is a phase that appears like an island with clear boundaries in the matrix of [ternary eutectic structure of Al/Zn/MgZn 2 ], and actually contains a small amount of Al in solid solution. Sometimes. As far as we can see from the phase diagram, it is thought that this phase does not contain any other additive elements, or even if they do, the amount is extremely small. [MgZn 2 phases] and MgZn 2 phases forming [ternary eutectic structure of Al/Zn/MgZn 2 ] can be clearly distinguished by microscopic observation.
  • the hot-dip plating layer according to this embodiment may not contain [MgZn two- phase] depending on the manufacturing conditions, but it is included in the hot-dip plating layer under most manufacturing conditions.
  • [Mg 2 Si phase] is a phase that appears in the form of islands with clear boundaries in the solidified structure of the hot-dip plating layer to which Si is added. As far as we can see from the phase diagram, it is thought that Zn, Al, and other additive elements are not solidly dissolved in the [Mg 2 Si phase], or even if they are solidly dissolved, the amount is extremely small. [Mg 2 Si phase] can be clearly distinguished from other phases in the hot-dip plating layer by microscopic observation.
  • the thickness of the hot-dip plating layer 2 formed on the steel plate 1 is t, and the thickness is 3t/4, t/2, or 3t/4 from the surface 2a of the hot-dip plating layer 2.
  • the exposed surfaces 3, 4, and 5 are cut out in a manner that is parallel to the surface 2a and has a width of 5 mm square in plan view at any position of t/4, these exposed surfaces
  • the area fraction of the [Zn phase] in the plating structure is less than 20%.
  • the area fraction of the [Zn phase] may be 15% or less, may be less than 15%, may be 10% or less, or may be 5% or less.
  • the area fraction of [Zn phase] is 20% or less, the proportion of fine glossy parts exhibiting metallic luster increases on the surface of the hot-dip plating layer, and the overall appearance of the hot-dip plating layer exhibits metallic luster. It begins to show itself. Further, the lower limit of the area fraction of [Zn phase] does not need to be particularly limited, but may be more than 0%, 1% or more, or 2% or more. Note that the schematic cross-sectional view shown in FIG. 1 is a cross-sectional view along the AA' plane of FIG. 2.
  • the ratio B (B/A (%)) is less than 20%.
  • the ratio (B/A (%)) may be 15% or less, less than 15%, or 10% or less.
  • the lower limit of the ratio (B/A (%)) is not particularly limited, but is 1% It may be more than 2%, or more than 5%.
  • the area fraction of the [Al phase] on the exposed surface where the area fraction of the [Zn phase] is measured may be, for example, 30 to 80 area %, or 40 to 65 area %.
  • the area fraction of [ternary eutectic structure of Al/MgZn 2 /Zn] on the exposed surface where the area fraction of [Zn phase] was measured may be, for example, 10 to 75 area %, or 20 to 75 area %. It may be 65 area%.
  • the area fraction of [MgZn 2 phase] on the exposed surface where the area fraction of [Zn phase] was measured may be, for example, 0 to 60 area %, or 10 to 40 area %.
  • the area fraction of [Mg 2 Si phase] on the exposed surface where the area fraction of [Zn phase] is measured may be, for example, 0 to 5 area %, or even 0 to 1 area %. good.
  • the hot-dip plating layer is scraped off by means such as argon sputtering or argon sputtering.
  • the exposed surface be a mirror surface, and for example, it is desirable that the maximum height Rz of the exposed surface be 0.2 ⁇ m or less.
  • the exposed surface to be observed may be an exposed surface at a depth of 3t/4 position, t/2 position, or t/4 position from the surface of the hot-dip plating layer.
  • the exposed surface at the t/2 position is selected.
  • the area fraction or B/A ratio of [Zn phase] satisfies the range of the present invention on the exposed surface at the t/2 position, the area fraction or B/A ratio of [Zn phase] will also be the same at other positions. is highly likely to satisfy the scope of the present invention. More preferably, in the exposed surface at a depth of any two of the 3t/4 position, t/2 position, or t/4 position from the surface of the hot-dip plating layer, the area fraction or B/A ratio of [Zn phase] is It is preferable that the scope of the invention be satisfied.
  • the area fraction or B/A ratio of the [Zn phase] is within the range of the present invention on the exposed surface at all depths from the surface of the hot-dip plating layer to the 3t/4 position, t/2 position, or t/4 position. It is good to satisfy the following.
  • the plating structure was observed using a secondary electron image of a scanning electron microscope (SEM) on an exposed surface of size 5 mm x 5 mm, and it was found that it was a [Zn phase] and a ternary eutectic structure of [Al/MgZn 2 /Zn]. ].
  • SEM scanning electron microscope
  • elemental analysis by an energy dispersive X-ray elemental analyzer attached to the SEM is used in combination, and the distributions of Zn, Al, and Mg are confirmed and specified.
  • the region where Zn is mainly detected is defined as the Zn phase
  • the region where Al is mainly detected is defined as the Al phase
  • the region where Zn and Mg are mainly detected is defined as the MgZn 2 phase.
  • the exposed surface parallel to the surface at any position of 3t/4, t/2 or t/4 from the surface of the hot-dip coating layer. It is necessary to control the structure of the hot-dip plating layer so that the area fraction of the [Zn phase] in .
  • the steel plate is immersed in a hot-dip plating bath with adjusted chemical components, thereby causing molten metal to adhere to the surface of the steel plate.
  • the steel plate is pulled out of the plating bath, and after controlling the amount of adhesion by gas wiping, the molten metal is solidified.
  • [Al phase] is first formed, and then as the temperature of the molten metal decreases, [ternary eutectic structure of Al/Zn/MgZn 2 ] is formed.
  • [MgZn 2 phase] and [Zn phase] are formed in the matrix of [ternary eutectic structure of Al/Zn/MgZn 2 ]. Furthermore, when Si is contained in the hot-dip plating layer, a [Mg 2 Si phase] is formed in the matrix of [ternary eutectic structure of Al/Zn/MgZn 2 ].
  • the present inventors have found that by increasing the number of Zn nucleation points, the formation of a coarse [Zn phase] can be suppressed and the quality of the surface appearance can be improved.
  • As a means for increasing the number of Zn nucleation points it is possible to attach a substance that can become a Zn nucleation point to the surface of the steel sheet that is the original plate. The details of the manufacturing method will be explained below.
  • Hot-rolled steel sheets and perform hot-rolled sheet annealing as necessary. After pickling, cold rolling is performed as necessary to obtain a cold rolled sheet. After degreasing and washing the hot-rolled sheet or cold-rolled sheet with water, the hot-rolled sheet or cold-rolled sheet is annealed, and the annealed hot-rolled sheet or cold-rolled sheet is immersed in a hot-dip plating bath to form a hot-dip plating layer.
  • Zn powder is attached to the annealed hot-rolled sheet or cold-rolled sheet before immersion in the hot-dip plating bath.
  • the attached Zn powder does not completely dissolve during hot-dip plating, and becomes a Zn nucleation site during final solidification of the plating.
  • Some Zn powder is diffused into the plating bath as a solid. In the manufacturing method of this embodiment, this is achieved only when Zn powder is attached after annealing and before immersion in a plating bath. If Zn powder is attached before annealing, Zn will alloy with the steel sheet during annealing, and the formation of a hot-dip plating layer will be inhibited.
  • the Zn powder to be deposited may be any Zn powder containing Zn and impurities.
  • the average particle size of the Zn powder may be, for example, in the range of 4 to 6 ⁇ m.
  • the amount of Zn powder deposited is preferably about 1 to 5 g/m 2 per side, for example. If the average particle size and the amount of adhesion are within this range, the Zn powder can function as a Zn nucleation site.
  • the Zn powder is preferably attached when the temperature of the hot-rolled or cold-rolled sheet is within the range of bath temperature +10°C to 20°C.
  • the hot-dip plating bath preferably contains Al: more than 10 to 22% by mass, Mg: 1.0 to 10% by mass, and the balance contains Zn and impurities. Further, the hot-dip plating bath may contain Si: 0.0001 to 2% by mass. Furthermore, the hot-dip plating bath contains any one of Ni, Ti, Zr, Sr, Fe, Sb, Pb, Sn, Ca, Co, Mn, P, B, Bi, Cr, Sc, Y, REM, Hf, and C. The total amount of the species or two or more species may be 0.0001 to 2% by mass.
  • the temperature of the hot-dip plating bath is preferably in the range of 400 to 500°C. This is because if the temperature of the hot-dip plating bath is within this range, a desired hot-dip plating layer can be formed. Further, the amount of the hot-dip coating layer to be deposited may be adjusted by means such as gas wiping on the steel sheet pulled out of the hot-dip coating bath. The amount of hot-dip plating layer deposited is preferably adjusted so that the total amount of deposit on both sides of the steel plate is in the range of 30 to 600 g/m 2 . If the amount of adhesion is less than 30 g/m 2 , the corrosion resistance of the Zn-Al-Mg hot-dip plated steel sheet will decrease, which is not preferable. If the amount of adhesion exceeds 600 g/m 2 , the molten metal adhering to the steel plate will sag, making it impossible to make the surface of the hot-dip plating layer smooth, which is not preferable.
  • the steel plate After adjusting the adhesion amount of the hot-dip plating layer, the steel plate is cooled. Cooling of the molten metal adhering to the steel plate is started after the steel plate is pulled up from the hot-dip plating bath. Although it depends on the composition of the hot-dip plating bath, the [Al phase] begins to crystallize around 430°C. Next, [MgZn 2 ] begins to crystallize from around 370°C, [ternary eutectic structure of Al/Zn/MgZn 2] begins to crystallize from around 340°C, and further [Zn phase] crystallizes, completing solidification. do.
  • the chemical conversion treatment is performed on the hot-dip galvanized steel sheet after the hot-dip plating layer has been formed.
  • the type of chemical conversion treatment is not particularly limited, and any known chemical conversion treatment can be used.
  • coating the hot-dip plated steel sheet after forming the hot-dip plating layer or after forming the chemical conversion treatment layer Perform processing.
  • the type of coating treatment is not particularly limited, and any known coating treatment can be used.
  • the metallic luster of the surface of the hot-dip plating layer can be improved more than before.
  • the plating structure was observed using a secondary electron image using a scanning electron microscope (SEM), and the plating structure was found to be [Zn phase] and [ternary eutectic of Al/MgZn 2 /Zn]. organization] was identified.
  • SEM scanning electron microscope
  • elemental analysis using an energy dispersive X-ray elemental analyzer attached to the SEM was also used, and the distribution of Zn, Al, and Mg was confirmed.
  • the area fraction of [Al phase] was in the range of 30 to 80 area %, and [ternary eutectic of Al/MgZn 2 /Zn
  • the area fraction of [structure] is in the range of 10 to 75 area %
  • the area fraction of [MgZn 2 phase] is in the range of 0 to 60 area %
  • the area fraction of [Mg 2 Si phase] is in the range of 0 to 75 area %. It was in the range of 5 area%.
  • A No appearance spots other than gloss are observed even from 0.5 m away.
  • B Appearance spots other than gloss are observed from 0.5 m away, but no appearance spots other than gloss are observed from 2 m away.
  • C Appearance spots other than gloss are observed even from 2 m away.
  • the corrosion resistance of the hot-dip plated steel sheet was evaluated by the corrosion weight loss after the CCT test.
  • a plated steel plate was cut into a size of 150 x 70 mm, and the corrosion weight loss after 30 cycles of CCT was investigated using CCT in accordance with JASO-M609.
  • a corrosion loss of less than 30 g/m 2 was evaluated as F
  • a corrosion loss of 30 g/m 2 or more and less than 50 g/m 2 was evaluated as G
  • a corrosion loss of 50 g/m 2 or more was evaluated as P
  • F and G were evaluated as passing.
  • the results are shown in Tables 2A and 2B.
  • the chemical composition of the hot-dip-coated layer was within the scope of the present invention, and because the Zn powder was attached after annealing and before hot-dip coating, the Zn powder was mixed at each Zn generation site when the hot-dip coating layer solidified.
  • the [Zn phase] of the plating structure on at least one exposed surface is ] was less than 20%. Therefore, the hot-dip plating layer had a shiny appearance. Moreover, the corrosion resistance was also good.
  • the hot-dip plated steel plate was annealed and hot-dipped after Zn powder was attached, so the Zn powder alloyed with the steel plate during annealing and did not function as a Zn nucleation site. Therefore, the area fraction of the [Zn phase] is all 20% or more at the 3t/4 position, t/2 position, or t/4 position from the surface of the hot-dip plating layer, and the appearance of the hot-dip plating layer is insufficiently glossy. Became.
  • the Zn-Al-Mg hot-dip plated steel sheet of the present disclosure has excellent metallic luster on the surface of the hot-dip plated layer and excellent corrosion resistance, so it has high industrial applicability.

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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)
PCT/JP2023/021552 2022-06-10 2023-06-09 Ｚｎ－Ａｌ－Ｍｇ系溶融めっき鋼板 Ceased WO2023238934A1 (ja)

Priority Applications (7)

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EP23819914.5A EP4538410A4 (en) 2022-06-10 2023-06-09 Zn-al-mg hot-dip plated steel sheet
US18/872,647 US20250369082A1 (en) 2022-06-10 2023-06-09 Zn-Al-Mg-BASED HOT-DIP PLATED STEEL SHEET
JP2024527033A JPWO2023238934A1 (https=) 2022-06-10 2023-06-09
KR1020247040945A KR20250010042A (ko) 2022-06-10 2023-06-09 Zn-Al-Mg계 용융 도금 강판
CN202380044360.9A CN119301292A (zh) 2022-06-10 2023-06-09 Zn-Al-Mg系热浸镀钢板
AU2023282694A AU2023282694A1 (en) 2022-06-10 2023-06-09 Zn-al-mg hot-dip plated steel sheet
MX2024014723A MX2024014723A (es) 2022-06-10 2024-11-27 Lamina de acero chapada por inmersion en caliente a base de zn-al-mg

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JP2004068075A (ja) 2002-08-06 2004-03-04 Jfe Steel Kk 加工性および耐食性に優れた溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板およびその製造方法
WO2020213686A1 (ja) * 2019-04-19 2020-10-22 日本製鉄株式会社 めっき鋼板
JP2021172878A (ja) * 2020-04-30 2021-11-01 日本製鉄株式会社 加工性と耐食性に優れる溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼材
JP2022094346A (ja) 2020-12-14 2022-06-24 クリンゲルンベルク・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 光学的歯車測定の方法および装置

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JP3179401B2 (ja) 1996-12-13 2001-06-25 日新製鋼株式会社 耐食性および表面外観の良好な溶融Ｚｎ−Ａｌ−Ｍｇめっき鋼板およびその製造法
JP3149129B2 (ja) 1997-03-04 2001-03-26 日新製鋼株式会社 耐食性および表面外観の良好な溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板およびその製造法
CN110268087B (zh) * 2017-01-27 2021-09-03 日本制铁株式会社 镀覆钢材
KR102235255B1 (ko) * 2017-12-26 2021-04-02 주식회사 포스코 내식성 및 표면 평활성이 우수한 아연합금도금강재 및 그 제조방법
KR20200051723A (ko) * 2017-12-28 2020-05-13 닛폰세이테츠 가부시키가이샤 도장 후 내식성이 우수한 용융 Zn계 도금 강판
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WO2003060179A1 (en) * 2002-01-09 2003-07-24 Nippon Steel Corporation Zinc-plated steel sheet excellent in corrosion resistance after coating and clarity of coating thereon
JP2004068075A (ja) 2002-08-06 2004-03-04 Jfe Steel Kk 加工性および耐食性に優れた溶融Ｚｎ−Ａｌ−Ｍｇ系めっき鋼板およびその製造方法
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JP2022094346A (ja) 2020-12-14 2022-06-24 クリンゲルンベルク・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング 光学的歯車測定の方法および装置

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TW202407116A (zh) 2024-02-16
US20250369082A1 (en) 2025-12-04
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