Plated steel sheets and parts containing them

Abstract

Provided are: a plated steel sheet that is provided with a base steel sheet and a plating layer disposed on the surface of the base steel sheet, and that is characterized in that the base steel sheet has a chemical composition containing, in mass%, 0.010-1.000% of Ni, 0.010-1.000% of Cu, and 0.003-1.000% of Sn, and the thickness of the plating layer in which the total concentration of Zn and / or Mn is at least 60 mass% is not less than 0.10 µm but less than 1.00 µm in an element distribution image obtained by measuring a cross-section of the plated steel sheet by using an EPMA; and a component including the plated steel sheet.

Description

[Technical Field]

[0001] This invention relates to plated steel sheets and parts containing the same. [Background technology]

[0002] It is known that improving the adhesion of coatings to steel sheets or plated steel sheets is effective in enhancing the chemical conversion treatment properties of the steel sheets or plated steel sheets, thereby uniformly forming a chemical conversion coating on these steel sheets.

[0003] In this regard, Patent Document 1 describes a continuous annealing furnace or a cold-rolled steel sheet / hot-dip galvanized steel sheet combined equipment with a continuous annealing furnace in which a cooling method for a cooling zone including part or all of the steel sheet temperature range of 600 to 250°C following heating for recrystallization is one or more of gas cooling, radiant cooling, or cooling tube cooling, in which high-strength cold-rolled steel sheets are continuously annealed, the steel sheet surface is exposed to an atmosphere in which iron oxidizes within the steel sheet temperature range, pickled at the exit side of the annealing furnace, and then coated with iron or Ni plating at a rate of 1 to 50 mg / m². 2 A method for manufacturing high-strength cold-rolled steel sheets, characterized by the application of a specific process, is described. Furthermore, Patent Document 1 explains that while oxidation of steel sheets is normally prevented by using an inert atmosphere with an extremely low concentration of oxygen and / or an extremely low dew point gas around the steel sheet, by instead actively exposing it to an oxidizing atmosphere, oxidizing not only Si and Mn but also the iron in the steel sheet, and then pickling it after it leaves the annealing furnace to remove the oxide film of Si, Mn, etc., along with the oxide film of iron in the steel sheet, as well as the oxide film of Si and Mn, etc., by pickling, a high-strength cold-rolled steel sheet with good chemical conversion treatment properties and no transparency can be obtained even with a high content of Si, Mn, etc.

[0004] Patent Document 2 describes a material containing 0.10% to 0.50% by mass of copper (Cu), with a surface residual scale count of 160,000 particles / mm². 2The following describes an automotive steel sheet characterized in that the maximum particle size of copper compound particles exposed on the surface is 2 μm or less. Furthermore, Patent Document 2 teaches that, according to the above configuration, the particle size of copper compound particles exposed on the steel sheet surface, which becomes the cathode point in the chemical conversion treatment, is made 2 μm or less, and the residual scale is made to a predetermined amount or less, thereby providing a steel sheet with excellent chemical conversion treatment properties. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2008-190030 [Patent Document 2] Japanese Patent Publication No. 2020-084238 [Overview of the project] [Problems that the invention aims to solve]

[0006] Patent Document 2 explains that, in addition to copper (Cu), elements such as nickel (Ni) and tin (Sn) reduce the mechanical properties required for automotive steel sheets, such as strength and formability, as well as chemical stability such as corrosion resistance. In particular, copper compounds present on the surface of steel sheets reduce the chemical conversion treatment properties necessary to improve corrosion resistance. Furthermore, generally, when the chemical conversion treatment properties decrease, areas where the chemical conversion coating, known as "skew," has not formed may occur, which can result in reduced paint adhesion.

[0007] Therefore, the present invention aims to provide a plated steel sheet containing Ni, Cu, and Sn that can exhibit improved coating adhesion, and a component containing the same. [Means for solving the problem]

[0008] To achieve the above objective, the inventors focused particularly on the plating layer and conducted investigations. As a result, the inventors discovered that coating the surface of a base steel sheet containing Ni, Cu, and Sn with a plating layer mainly containing at least one of Zn and Mn to a predetermined thickness can significantly improve coating adhesion, thus completing the present invention.

[0009] The present invention, which has achieved the above objectives, is as follows. (1) A plated steel sheet comprising a base steel sheet and a plating layer disposed on the surface of the base steel sheet, The aforementioned base steel plate is, by mass%, Ni: 0.010~1.000%, Cu: 0.010~1.000%, and It has a chemical composition containing Sn: 0.003 to 1.000%, In the elemental distribution image obtained by measuring the cross-section of the plated steel sheet with EPMA, A plated steel sheet characterized by having a plating layer thickness of 0.10 to less than 1.00 μm, wherein the total concentration of at least one of Zn and Mn is 60% by mass or more. (2) The plated steel sheet according to (1) above, characterized in that the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn is 60% by mass or more, is 0.30 to less than 1.00 μm. (3) The plated steel sheet according to (2) above, characterized in that the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn is 60% by mass or more, is 0.50 to less than 1.00 μm. (4) The chemical composition is, in mass%, Ni: 0.040~1.000%, Cu: 0.040~1.000%, and Sn: 0.004~1.000% A plated steel sheet according to any one of the above items (1) to (3), characterized by including the following. (5) A plated steel sheet according to any one of the above items (1) to (4), characterized by having a Vickers hardness of 200 Hv or more. A component comprising the plated steel sheet according to any one of (1) to (5) above.

Advantages of the Invention

[0010] According to the present invention, there can be provided a plated steel sheet containing Ni, Cu, and Sn, which can exhibit improved coating adhesion, and a component including the same.

Embodiments for Carrying Out the Invention

[0011] <Plated Steel Sheet> The plated steel sheet according to an embodiment of the present invention is a plated steel sheet including a base steel sheet and a plating layer disposed on the surface of the base steel sheet, where the base steel sheet has, in mass%, Ni: 0.010 to 1.000%, Cu: 0.010 to 1.000%, and Sn: 0.003 to 1.000% and has a chemical composition, in an element distribution image obtained by measuring a cross-section of the plated steel sheet by EPMA, the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more is less than 0.10 to 1.00 μm.

[0012] As described above, generally, when the chemical conversion treatment property deteriorates, there may occur a region where a chemical conversion treatment film called ske is not formed, and as a result, the coating adhesion may deteriorate. For example, when elements such as Ni, Cu, and Sn are dissolved in the steel sheet, the potential of the steel sheet becomes nobler compared to the state where these elements are not dissolved, and the etching property of Fe may deteriorate during the chemical conversion treatment. In this case, the chemical conversion treatment property of the steel sheet deteriorates, and as a result, the coating adhesion deteriorates. Therefore, when the steel sheet contains the three elements of Ni, Cu, and Sn at the same time, such a decrease in coating adhesion becomes a particularly problematic issue.

[0013] As methods for manufacturing steel sheets, for example, there are generally known two methods: a method of obtaining molten iron in a blast furnace using iron ore, which is a natural resource, as the main raw material, and then producing molten steel through refining in a converter or the like; and a method of producing molten steel in an electric furnace using scrap materials, which are recycled resources, as the main raw material. Since blast furnace materials can also contain elements such as Ni, Cu, and Sn as additive elements, when these elements are contained, it is necessary to appropriately address the above problems. On the other hand, since electric furnace materials use scrap materials as the main raw material as described above, they contain a relatively large amount of scrap-derived elements such as Ni, Cu, and Sn (so-called trump elements), and therefore the above problems become particularly prominent.

[0014] Therefore, the inventors of the present invention focused particularly on the plating layer in order to provide a plated steel sheet that can exhibit excellent coating adhesion even when the steel sheet contains three elements, Ni, Cu, and Sn, simultaneously, and conducted studies. As a result, the inventors of the present invention found that it is effective to coat the surface of a base steel sheet containing Ni, Cu, and Sn with a plating layer mainly containing at least one of Zn and Mn to a predetermined thickness.

[0015] More specifically, Zn and Mn function as anodes during chemical conversion treatment and improve the chemical conversion treatment properties of steel sheets by dissolving themselves. Therefore, even if the base steel sheet contains Ni, Cu, and Sn, if the manufacturing method is appropriately controlled and the surface of the base steel sheet is properly coated with a plating layer mainly containing at least one of Zn and Mn, it is possible to significantly improve the chemical conversion treatment properties of the plated steel sheet. Thus, the inventors first found that by appropriately controlling the manufacturing method, as will be explained in detail later, it is possible to suppress the formation of oxides, particularly Mn and / or Si-based surface oxides, on the surface of a base steel sheet containing Ni, Cu, and Sn, and thereby coat the surface of the base steel sheet with a plating layer mainly containing at least one of Zn and Mn. In addition, the inventors have found that by controlling the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more, when the cross-section of the plated steel sheet is measured with EPMA (electron probe microanalyzer), the chemical conversion treatment properties of the plated steel sheet can be significantly improved. Therefore, in the plated steel sheet according to the embodiment of the present invention, even though the base steel sheet contains three elements, Ni, Cu, and Sn, the anode dissolution (etching) of Zn and / or Mn in the plating layer can be promoted during the chemical conversion treatment, allowing for the uniform formation of a chemical conversion treatment film over the entire steel sheet, and as a result, the adhesion of the coating film can be significantly improved.

[0016] The plated steel sheets according to the embodiments of the present invention encompass not only electric furnace materials that inevitably contain Ni, Cu, and Sn as trump elements, but also blast furnace materials that contain Ni, Cu, and Sn as essential or optional additive elements. Furthermore, the plated steel sheets according to the embodiments of the present invention can achieve superior coating adhesion and, consequently, superior corrosion resistance compared to conventional plated steel sheets that simultaneously contain all three elements: Ni, Cu, and Sn. Therefore, the plated steel sheets according to the embodiments of the present invention are particularly useful in the automotive sector where excellent coating adhesion and / or corrosion resistance are required. The components of the plated steel sheets according to the embodiments of the present invention will be described in more detail below.

[0017] [Plating layer] According to embodiments of the present invention, the plating layer is disposed on the surface of the base steel sheet, for example, on at least one, preferably both, surfaces of the base steel sheet. The plating layer only needs to contain at least one of Zn and Mn and satisfy the requirements for the concentrations of Zn and Mn and the thickness of the plating layer, which will be described in detail later, and therefore can encompass a variety of plating compositions. Accordingly, the plating layer may contain other elements in addition to Zn and Mn, such as Al, Ni, Cu, Sn, Mg, and Fe. More specifically, the plating layer may contain or be composed of Zn-Cu and / or Zn-Fe, etc. Naturally, the plating layer may essentially consist of at least one of Zn and Mn, consist of at least one of Zn and Mn, or be composed of at least one of Zn and Mn. The amount of plating deposited is not particularly limited and should be appropriately selected within a range that satisfies the requirements for the concentrations of Zn and Mn and the thickness of the plating layer, which will be described in detail later.

[0018] [Plating layer thickness where the combined concentration of at least one of Zn and Mn is 60% by mass or more: 0.10 to less than 1.00 μm] In embodiments of the present invention, the thickness of the plating layer in which the total concentration of at least one element, Zn and Mn, is 60% by mass or more, as shown in the elemental distribution image obtained by measuring the cross-section of the plated steel sheet with EPMA, is controlled to less than 0.10 to 1.00 μm. As mentioned above, Zn and Mn function as anodes during chemical conversion treatment and improve the chemical conversion treatment properties of the steel sheet by dissolving themselves. In embodiments of the present invention, by controlling the thickness of the plating layer in which the total concentration of at least one element, Zn and Mn, is 60% by mass or more, to less than 0.10 to 1.00 μm, it becomes possible to effectively utilize Zn and Mn in the plating layer as anodes during chemical conversion treatment. That is, the anodic dissolution (etching) of Zn and / or Mn in the plating layer during chemical conversion treatment is promoted, allowing the chemical conversion treatment film to be uniformly formed over the entire steel sheet, and as a result, the adhesion of the coating film can be significantly improved. From the viewpoint of further improving coating adhesion, the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more is preferably as thick as possible, for example, preferably 0.20 μm or more or 0.30 μm or more, more preferably 0.40 μm or more or 0.50 μm or more, and most preferably 0.60 μm or more or 0.70 μm or more. On the other hand, if the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more becomes too thick, the workability of the plated steel sheet may decrease, or the P ratio in the film obtained by the phosphorylation treatment may decrease, resulting in reduced coating adhesion. To explain the latter in more detail, the P ratio represents the ratio of phopite (Zn3(PO4)2·4H2O) to phosphophyllite (Zn2Fe(PO4)2·4H2O) in the film obtained by the phosphorylation treatment, and more specifically, the X-ray diffraction intensity of the (100) plane of phosphophyllite measured using an X-ray diffractometer I P X-ray diffraction intensity I of the (020) plane of hopite H Using I P / ( I P +I HThis refers to the value expressed as ) × 100 (%). A higher P ratio means that a larger amount of Fe-containing phosphophyllite is present, and that phosphophyllite crystals are densely formed on the steel sheet surface. It is also generally known that a lower P ratio reduces the adhesion of the coating film. Here, the Fe in the phosphophyllite originates from the Fe in the base steel sheet that was dissolved during the chemical conversion treatment. Therefore, if Fe is not sufficiently dissolved during the chemical conversion treatment, the formation of phosphophyllite is not promoted, and the P ratio value becomes smaller. In the embodiment of the present invention, if the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more becomes too thick, the amount of Fe dissolved from the base steel sheet during the chemical conversion treatment decreases. As a result, the P ratio of the resulting chemical conversion treated film decreases, and the adhesion of the coating film decreases. Therefore, the thickness of the plating layer should be less than 1.00 μm, and may be 0.95 μm or less or 0.90 μm or less.

[0019] [Measurement of the thickness of a plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more] The thickness of a plating layer in which the combined concentration of at least one of Zn and Mn is 60% by mass or more is measured by EPMA as follows. First, five samples are taken from the surface of the plated steel sheet so that the cross-section of the plated steel sheet can be observed. Next, for each sample, a rectangular area of ​​80 μm in the thickness direction and 100 μm in the direction perpendicular to the thickness direction is defined as one field of view, and an EPMA (e.g., JXA-8500 manufactured by JEOL Ltd.) is used for a total of five fields of view for the five samples, with an acceleration voltage of 15 kV and an irradiation current of 5 × 10⁻¹⁰ -7 Under conditions A, images are taken at 1000x magnification to obtain a mapping image. Next, in the obtained elemental distribution image, a region on the surface of the plated steel sheet where the total concentration of at least one element, Zn and Mn, is 60% by mass or more is determined, and the area of ​​this region is divided by the length (100 μm) perpendicular to the thickness direction of the field of view to determine the thickness of the plating layer in one sample. Finally, the average of the thicknesses obtained for five samples is calculated, and this calculated value is determined as the thickness of the plating layer where the total concentration of at least one element, Zn and Mn, is 60% by mass or more.

[0020] [Base material steel plate] In embodiments of the present invention, the base steel sheet has a chemical composition comprising, by mass%, Ni: 0.010 to 1.000%, Cu: 0.010 to 1.000%, and Sn: 0.003 to 1.000%. As described above, the present invention aims to provide a plated steel sheet containing Ni, Cu, and Sn that can exhibit improved coating adhesion. This objective is achieved by controlling the thickness of the plating layer to less than 0.10 to 1.00 μm, where the combined concentration of at least one of Zn and Mn is 60% by mass or more, when the cross-section of the plated steel sheet is measured by EPMA. Therefore, the chemical composition of the base steel sheet is not particularly limited other than containing, by mass%, Ni: 0.010 to 1.000%, Cu: 0.010 to 1.000%, and Sn: 0.003 to 1.000%, and it is clear that elements other than Ni, Cu, and Sn are not essential technical features for achieving the objective of the present invention. The chemical composition of the base steel sheet can include Ni, Cu, and Sn, in appropriate amounts, any alloying elements commonly added in the art of the present invention. The chemical composition of the base steel sheet used in plated steel sheets according to embodiments of the present invention will be described in detail below, but these descriptions are intended merely as examples of preferred chemical compositions of base steel sheets for application in automotive steel sheets and the like, and are not intended to limit the present invention to those using base steel sheets having such specific chemical compositions.

[0021] In embodiments of the present invention, for example, the base steel sheet is, by mass%, C: 0.001~0.500%, Si: 0~3.00%, Mn: 0.10~3.00%, Al: 0.001~2.000%, Ni: 0.010~1.000%, Cu: 0.010~1.000%, Sn: 0.003~1.000%, P: 0.100% or less, S: 0.100% or less, N: 0.0100% or less, Ti: 0~0.150%, Nb: 0~0.150%, B: 0~0.0100%, Mo: 0~1.000%, Cr: 0~1.000%, V: 0~0.150%, W: 0~1.000%, Hf: 0~0.050%, Mg: 0~0.050%, Zr: 0~0.050%, Ca: 0~0.010%, REM: 0~0.010%, As: 0~0.010%, Ir: 0~1.000%, and Remainder: Fe and impurities It is preferable to have a chemical composition consisting of the following. Each element will be described in more detail below.

[0022] [C:0.001~0.500%] Carbon (C) is an element that increases strength inexpensively and is an important element for controlling the strength of steel. To obtain this effect fully, it is preferable that the C content be 0.001% or more. The C content may also be 0.005% or more, 0.010% or more, 0.030% or more, 0.040% or more, 0.070% or more, 0.100% or more, 0.150% or more, or 0.200% or more. On the other hand, excessive C content may lead to a decrease in elongation. For this reason, it is preferable that the C content be 0.500% or less. The C content may also be 0.450% or less, 0.400% or less, 0.350% or less, 0.300% or less, or 0.250% or less.

[0023] [Si: 0~3.00%] Si is an effective element for increasing strength as a solid solution strengthening element. The Si content may be 0%, but to obtain such an effect, it is preferable that the Si content be 0.01% or more. The Si content may be 0.05% or more, 0.10% or more, 0.30% or more, 0.50% or more, 0.80% or more, or 1.00% or more. On the other hand, if the Si content is excessive, it may lead to a decrease in elongation along with an increase in steel strength. For this reason, it is preferable that the Si content be 3.00% or less. The Si content may be 2.50% or less, 2.00% or less, 1.50% or less, or 1.20% or less.

[0024] [Mn: 0.10~3.00%] Mn is an element that enhances the hardenability of steel and is effective in increasing its strength. To fully obtain these effects, it is preferable that the Mn content be 0.10% or more. The Mn content may also be 0.50% or more, 1.00% or more, 1.30% or more, 1.50% or more, or 1.80% or more. On the other hand, if the Mn content is excessive, it may lead to a decrease in elongation along with an increase in steel strength. For this reason, it is preferable that the Mn content be 3.00% or less. The Mn content may also be 2.80% or less, 2.50% or less, or 2.00% or less.

[0025] [Al:0.001~2.000%] Al acts as a deoxidizing agent for steel and is an element that has the effect of sounding down steel. To obtain this effect sufficiently, it is preferable that the Al content be 0.001% or more. The Al content may be 0.005% or more, 0.010% or more, 0.020% or more, or 0.030% or more. On the other hand, if the Al content is excessive, coarse Al oxide may be generated, which may reduce the elongation of the steel sheet. For this reason, it is preferable that the Al content be 2.000% or less. The Al content may be 1.500% or less, 1.000% or less, 0.500% or less, 0.100% or less, or 0.050% or less.

[0026] [Ni: 0.010~1.000%] [Cu: 0.010~1.000%] Ni and Cu are elements that contribute to improving strength through precipitation strengthening or solid solution strengthening. To fully obtain such effects, the content of each of these elements is preferably 0.010% or more, and may be 0.020% or more, 0.030% or more, 0.040% or more, 0.050% or more, 0.080% or more, 0.100% or more, 0.150% or more, or 0.200% or more. On the other hand, if these elements are present in excess, it may promote the formation of oxides on the surface of the steel sheet, particularly Mn and / or Si-based surface oxides and iron oxides, in which case the adhesion of the plating in the plating process will be inhibited. Therefore, the content of Ni and Cu is preferably 1.000% or less, and may be 0.800% or less, 0.600% or less, 0.400% or less, or 0.300% or less.

[0027] [Sn: 0.003~1.000%] Sn is an effective element for improving corrosion resistance. To obtain this effect fully, the Sn content is preferably 0.003% or more. The Sn content may be 0.004% or more, 0.008% or more, 0.010% or more, 0.020% or more, 0.030% or more, 0.040% or more, 0.050% or more, 0.080% or more, or 0.100% or more. On the other hand, if the Sn content is excessive, it may promote the formation of oxides on the surface of the steel sheet, particularly Mn and / or Si-based surface oxides and iron oxides, which may hinder the adhesion of the plating in the plating process. Therefore, the Sn content is preferably 1.000% or less. The Sn content may be 0.800% or less, 0.600% or less, 0.400% or less, 0.300% or less, or 0.200% or less.

[0028] [P:0.100% or less] P is an element that segregates at grain boundaries and promotes steel embrittlement. A lower P content is preferable, and ideally it should be 0%. However, excessive reduction of the P content can lead to a significant increase in cost. For this reason, the P content may be 0.0001% or more, or 0.001% or more, or 0.005% or more. On the other hand, excessive P content can lead to steel embrittlement due to grain boundary segregation, as described above. Therefore, it is preferable to have a P content of 0.100% or less. The P content may also be 0.050% or less, 0.030% or less, 0.020% or less, or 0.010% or less.

[0029] [S:0.100% or less] S is an element that generates nonmetallic inclusions such as MnS in steel, leading to a decrease in the ductility of steel parts. A lower S content is preferable, and ideally it should be 0%. However, excessive reduction of the S content can lead to a significant increase in cost. For this reason, the S content may be 0.0001% or more, 0.0005% or more, 0.001% or more, or 0.002% or more. On the other hand, excessive S content can lead to cracking during cold forming, originating from nonmetallic inclusions. Therefore, it is preferable to have an S content of 0.100% or less. The S content may also be 0.050% or less, 0.020% or less, or 0.010% or less.

[0030] [N:0.0100% or less] N is an element that forms coarse nitrides in steel sheets, reducing their workability. A lower N content is preferable, ideally 0%. However, excessive reduction of the N content can lead to a significant increase in manufacturing costs. Therefore, the N content may be 0.0001% or higher, or 0.0005% or higher, or 0.0010% or higher. On the other hand, excessive N content can lead to the formation of coarse nitrides, as described above, reducing the workability of the steel sheet. Therefore, the N content is preferably 0.0100% or less. The N content may also be 0.0080% or less, 0.0060% or less, or 0.0050% or less.

[0031] The preferred basic chemical composition of the base steel sheet is as described above. Furthermore, the base steel sheet may, if necessary, contain at least one of the following elements in place of a portion of the remaining Fe.

[0032] [Ti: 0~0.150%] [Nb: 0~0.150%] [V: 0~0.150%] Ti, Nb, and V have the effect of improving the strength of steel sheets by forming carbonitrides in the steel and strengthening through precipitation. The Ti, Nb, and V content may be 0%, but in order to obtain such an effect, the Ti, Nb, and V content is preferably 0.001% or more, and may be 0.002% or more, 0.005% or more, or 0.010% or more. On the other hand, if these elements are included in excess, the effect will saturate, and including them in the steel more than necessary will lead to an increase in manufacturing costs. Therefore, the Ti, Nb, and V content is preferably 0.150% or less, and may be 0.120% or less, 0.100% or less, 0.080% or less, 0.050% or less, 0.020% or less, or 0.015% or less.

[0033] [B: 0~0.0100%] B improves low-temperature toughness by segregating at grain boundaries and increasing grain boundary strength. The B content may be 0%, but to obtain this effect, it is preferable that the B content be 0.0001% or more. The B content may also be 0.0002% or more, 0.0005% or more, or 0.0010% or more. On the other hand, if the B content is excessive, the effect will saturate, which may lead to an increase in manufacturing costs. Therefore, it is preferable that the B content be 0.0100% or less. The B content may also be 0.0050% or less, 0.0030% or less, 0.0020% or less, or 0.0015% or less.

[0034] [Mo: 0~1.000%] [Cr: 0~1.000%] [W: 0~1.000%] Mo, Cr, and W are elements that enhance the hardenability of steel and contribute to improving its strength. While the content of Mo, Cr, and W may be 0%, to obtain such effects, it is preferable that the content of Mo, Cr, and W be 0.001% or more, and may be 0.010% or more, 0.020% or more, or 0.030% or more. On the other hand, if these elements are included in excess, the effect will saturate, and including them in the steel more than necessary will lead to an increase in manufacturing costs. Therefore, it is preferable that the content of Mo, Cr, and W be 1.000% or less, and may be 0.500% or less, 0.100% or less, 0.050% or less, or 0.040% or less.

[0035] [Hf: 0~0.050%] [Mg: 0~0.050%] [Zr:0~0.050%] [Ca: 0~0.010%] [REM: 0~0.010%] Hf, Mg, Zr, Ca, and REM are elements that can control the morphology of nonmetallic inclusions. The content of Hf, Mg, Zr, Ca, and REM may be 0%, but to obtain such an effect, the content of each of these elements is preferably 0.0001% or more, and may be 0.0005% or more, or 0.001% or more. On the other hand, if these elements are included in excess, the effect will saturate, and including them in the steel sheet more than necessary will lead to an increase in manufacturing costs. Therefore, the content of Hf, Mg, and Zr is preferably 0.050% or less, and may be 0.010% or less, 0.005% or less, or 0.003% or less, respectively. Similarly, the content of Ca and REM is preferably 0.010% or less, and may be 0.005% or less, or 0.003% or less, respectively.

[0036] [As: 0~0.010%] As is an effective element for improving corrosion resistance. While the As content may be 0%, it is preferable that the As content be 0.001% or more to obtain this effect. The As content may also be 0.002% or more, or 0.003% or more. On the other hand, if the As content is excessive, the effect will saturate, and including more As than necessary in the steel sheet will lead to an increase in manufacturing costs. Therefore, it is preferable that the As content be 0.010% or less. The As content may also be 0.008% or less, or 0.005% or less.

[0037] [Ir: 0~1.000%] Ir is an element that segregates at prior austenite grain boundaries, increasing their strength. While the Ir content may be 0%, it is preferable that the Ir content be 0.001% or higher to obtain this effect. The Ir content may also be 0.003% or higher, 0.005% or higher, or 0.010% or higher. On the other hand, excessive Ir content leads to saturation of the effect, and including more Ir than necessary in the steel increases manufacturing costs. Therefore, it is preferable that the Ir content be 1.000% or lower. The Ir content may also be 0.500% or lower, 0.100% or lower, 0.030% or lower, or 0.015% or lower.

[0038] In the base steel sheet, the remainder other than the elements mentioned above consists of Fe and impurities. Impurities in the base steel sheet refer to components that are mixed in during the industrial production of the base steel sheet due to various factors in the manufacturing process, including raw materials such as ore and scrap.

[0039] The chemical composition of the base steel sheet can be measured using general analytical methods. For example, the chemical composition of the base steel sheet can be determined by first removing the plating layer by mechanical grinding, and then measuring the chips using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry) in accordance with JIS G 1201:2014. Specifically, for example, a 35 mm square test piece can be obtained from around the 1 / 2 thickness point of the base steel sheet, and the composition can be determined by measuring it using a Shimadzu ICPS-8100 or similar (measuring device) under conditions based on a pre-established calibration curve. C and S, which cannot be measured by ICP-AES, can be measured using the combustion-infrared absorption method, and N can be measured using the inert gas fusion-thermal conductivity method.

[0040] [Thickness of the base steel plate] The thickness of the base steel sheet is not particularly limited, but generally it is between 0.2 and 8.0 mm. For example, the thickness may be 0.3 mm or more, 0.6 mm or more, 1.0 mm or more, 1.6 mm or more, or 2.0 mm or more. Similarly, the thickness of the base steel sheet may be, for example, 7.0 mm or less, 6.0 mm or less, 5.0 mm or less, or 4.0 mm or less.

[0041] As described above, the steel sheet according to the embodiment of the present invention can achieve superior coating adhesion and, consequently, superior corrosion resistance compared to conventional plated steel sheets containing the three elements Ni, Cu, and Sn simultaneously. Therefore, the plated steel sheet according to the embodiment of the present invention is useful for use in parts in technical fields where excellent coating adhesion and / or corrosion resistance are required, and is particularly useful for use in automotive parts. In a preferred embodiment, an automotive part including the plated steel sheet according to the embodiment of the present invention is provided. Examples of automotive parts include frame parts, bumpers, other structural and reinforcing parts requiring strength, and exterior parts such as roofs, hoods, fenders, and doors where high aesthetic appeal is required. These parts only need to include the plated steel sheet according to the embodiment of the present invention in at least a portion of them, and therefore at least a portion of these parts will satisfy the characteristics of the plated steel sheet described above. In forming processes such as press forming, the characteristics of the plated steel sheet do not particularly change before and after forming in parts of the steel sheet that do not directly contact the mold or, even if they do, have a relatively low degree of processing.

[0042] [Mechanical properties] The plated steel sheet according to the embodiment of the present invention is not particularly limited, but may have a Vickers hardness of, for example, 90 Hv or higher. The Vickers hardness may be 150 Hv or higher, 200 Hv or higher, 250 Hv or higher, 300 Hv or higher, 350 Hv or higher, 400 Hv or higher, or 450 Hv or higher. The upper limit is not particularly limited, but for example, the Vickers hardness may be 650 HV or lower, 600 HV or lower, 550 HV or lower, or 500 HV or lower.

[0043] [Measurement of Vickers hardness] Vickers hardness is determined as follows: First, a test piece is cut from any position on the plated steel sheet, excluding the edges, so that a cross-section perpendicular to the surface (thickness cross-section) can be observed. The thickness cross-section of the test piece is polished using #600 to #1500 silicon carbide sandpaper, and then polished to a mirror finish using a liquid in which diamond powder with a particle size of 1 to 6 μm is dispersed in a diluent such as alcohol or pure water. This thickness cross-section is used as the measurement surface. Next, the Vickers hardness is measured using a micro Vickers hardness tester with a load of 1 kgf at intervals of at least three times the indentation length. Specifically, a total of 20 points are randomly measured around the 1 / 2 position of the plated steel sheet thickness, and the arithmetic mean of these measurements is determined as the Vickers hardness of the plated steel sheet.

[0044] <Method for manufacturing plated steel sheets> Next, preferred manufacturing methods for plated steel sheets according to embodiments of the present invention will be described. The following description is intended to illustrate characteristic methods for manufacturing plated steel sheets according to embodiments of the present invention, and is not intended to limit the plated steel sheets to those manufactured by the manufacturing methods described below.

[0045] A plated steel sheet according to an embodiment of the present invention can be manufactured by, for example, a casting step of casting molten steel with an adjusted chemical composition to form a steel billet, a hot rolling step of hot rolling the steel billet to obtain a hot-rolled steel sheet, a winding step of winding the hot-rolled steel sheet and then performing primary pickling, a cold rolling step of cold rolling the winded hot-rolled steel sheet to obtain a cold-rolled steel sheet, an annealing step of annealing the cold-rolled steel sheet, a secondary pickling step of secondary pickling the annealed cold-rolled steel sheet, and a plating step of applying plating to the obtained base steel sheet. The following describes in detail the manufacturing of a plated steel sheet obtained by plating a cold-rolled steel sheet, but the plated steel sheet according to an embodiment of the present invention includes not only plated steel sheets obtained by plating a cold-rolled steel sheet, but also plated steel sheets obtained by plating a hot-rolled steel sheet. Therefore, when manufacturing a plated steel sheet obtained by plating a hot-rolled steel sheet, for example, the secondary pickling step may be performed after the winding step without performing the cold rolling step and annealing step described below. Each step will be described in detail below.

[0046] [Casting Process] The conditions for the casting process are not particularly limited. For example, after melting in a blast furnace or electric furnace, various secondary smelting processes may be carried out, followed by casting using methods such as conventional continuous casting or ingot casting.

[0047] [Hot rolling process] Hot-rolled steel sheets can be obtained by hot-rolling cast steel billets. The hot-rolling process is carried out by hot-rolling the cast steel billet either directly or after it has been cooled and then reheated. When reheating is performed, the heating temperature of the steel billet may be, for example, 1100 to 1250°C. In the hot-rolling process, rough rolling and finish rolling are usually performed. The temperature and reduction ratio of each rolling step can be appropriately determined according to the desired metal structure and sheet thickness. For example, the finishing temperature of the finish rolling may be 900 to 1050°C, and the reduction ratio of the finish rolling may be 10 to 50%.

[0048] [Winding process] The hot-rolled steel sheet obtained in the hot-rolling process is wound in the next winding process and then subjected to primary pickling. In this manufacturing method, the winding of the hot-rolled steel sheet is carried out at a winding temperature of 520°C or higher. By controlling the winding temperature to 520°C or higher, an external oxide layer is formed on the outside (surface) of the steel sheet, and an internal oxide layer is also formed inside (surface) of the steel sheet. This internal oxide layer is mainly composed of Mn and / or Si-based oxides. Therefore, directly beneath the internal oxide layer formed on the surface of the steel sheet, a Mn-Si depleted layer is formed due to the consumption of Mn and / or Si in the steel by the formation of the internal oxide layer. In particular, by controlling the winding temperature to 520°C or higher, the thickness of the Mn-Si depleted layer can be controlled to 0.3 μm or more. Since the above-mentioned external and internal oxide layers are removed by primary pickling after winding, a Mn-Si depleted layer with a thickness of 0.3 μm or more remains on the surface of the hot-rolled steel sheet after primary pickling. By forming the surface of the hot-rolled steel sheet with a Mn-Si deficient layer having a thickness of 0.3 μm or more, the deficient Mn and Si on the steel sheet surface effectively suppresses the formation of Mn and / or Si-based surface oxides on the steel sheet surface during the subsequent annealing process. Consequently, the subsequent plating process can be carried out appropriately, and the final plated steel sheet can be plated to a desired thickness with a total concentration of at least one of Zn and Mn of 60% by mass or more.

[0049] The thickness of the Mn-Si depletion layer is determined as follows. First, using a radiofrequency glow discharge emission spectrometer (GDS), the surface of the steel sheet after primary pickling is subjected to an Ar atmosphere, and a voltage is applied to generate a glow plasma. The surface of the steel sheet is then sputtered and analyzed in the depth direction. The elements contained in the material are identified from the emission spectral wavelengths of the elements emitted when atoms are excited in the glow plasma, and the emission intensity of the identified elements is estimated. The data in the depth direction can be estimated from the sputtering time. Specifically, by determining the relationship between sputtering time and sputtering depth using a standard sample beforehand, the sputtering time can be converted to sputtering depth. Therefore, the sputtering depth converted from sputtering time can be defined as the depth from the surface of the material. The obtained emission intensity is converted to mass % by creating a calibration curve. In this way, when the steel sheet after primary pickling is measured by GDS, the region in the depth direction where the sum of the Mn concentration and Si concentration is 70% or less of the sum of the Mn concentration and Si concentration at the 1 / 2 position of the sheet thickness is defined as the Mn-Si depletion layer, and its thickness is determined.

[0050] The primary pickling is not particularly limited and should be carried out using a commonly used pickling solution under conditions suitable for removing the external and internal oxide layers. The primary pickling may be performed once or in multiple steps to ensure the complete removal of the external and internal oxide layers.

[0051] In steel sheets containing the three elements Ni, Cu, and Sn simultaneously, the presence of these elements in the steel sheet may promote the formation of Mn and / or Si-based surface oxides on the steel sheet surface. Therefore, it is extremely difficult to suppress the formation of such surface oxides and properly adhere plating to steel sheets containing the three elements Ni, Cu, and Sn simultaneously. However, with this manufacturing method, by combining a Mn-Si deficient layer formed to a predetermined thickness, i.e., 0.3 μm or more, due to appropriate control of the winding temperature in the winding process, with a secondary pickling process which will be explained in detail later, it is possible to significantly suppress the formation of such surface oxides. On the other hand, if the winding temperature in the winding process is less than 520°C, the formation of the internal oxide layer will be insufficient, and as a result, it will not be possible to form a Mn-Si deficient layer with a thickness of 0.3 μm or more. In this case, it will not be possible to sufficiently suppress the formation of Mn and / or Si-based surface oxides in the annealing process, and it will be difficult to properly adhere the plating in the subsequent plating process. As a result, it becomes impossible to form a plating layer of the desired thickness in the final plated steel sheet in which the total concentration of at least one of Zn and Mn is 60% by mass or more.

[0052] From the viewpoint of further improving coating adhesion by increasing the thickness of the plating layer in which the combined concentration of at least one of Zn and Mn is 60% by mass or more, it is preferable to control the winding temperature to 550°C or higher. By controlling the winding temperature to 550°C or higher, the formation of the internal oxide layer can be further promoted, which in turn makes it possible to make the Mn-Si depleted layer thicker. As a result, the formation of Mn and / or Si-based surface oxides in the annealing process can be suppressed even more significantly, making it possible to further increase the thickness of the plating layer. The upper limit of the winding temperature is not particularly limited, but for example, the winding temperature may be 600°C or lower.

[0053] [Cold rolling process] After pickling or performing other processes on hot-rolled steel sheets, cold-rolled steel sheets can be obtained by cold-rolling them. The reduction ratio during cold rolling can be appropriately determined according to the desired metal structure and sheet thickness, and may be, for example, 20-80%. After the cold-rolling process, the sheet may be cooled to room temperature by air cooling, for example.

[0054] [Annealing process] Next, the obtained cold-rolled steel sheet is annealed. The annealing process involves heating the cold-rolled steel sheet to a temperature of 700 to 950°C in an atmosphere with a dew point of -40 to 20°C and holding it for 0 to 300 seconds. The atmosphere in the annealing process may be a reducing atmosphere, more specifically a reducing atmosphere containing nitrogen and hydrogen, for example, a reducing atmosphere with 1 to 10% hydrogen (e.g., a balance of 4% hydrogen and nitrogen).

[0055] [Secondary pickling process] The annealed cold-rolled steel sheet is subjected to a secondary pickling process. Specifically, the secondary pickling process involves immersing the cold-rolled steel sheet in an aqueous solution with a hydrochloric acid concentration of 3-12% that does not contain inhibitors to suppress corrosion of the steel sheet, at a temperature of 50-90°C for 2-100 seconds, and then washing the cold-rolled steel sheet with a water washing solution having an electrical conductivity of 40 mS / m or less. This secondary pickling using an aqueous hydrochloric acid solution can sufficiently or completely remove the Mn and / or Si-based surface oxides formed on the surface of the cold-rolled steel sheet during the annealing process. More specifically, by forming a predetermined Mn-Si deficient layer in the winding process, the formation of Mn and / or Si-based surface oxides in the annealing process can be sufficiently suppressed compared to the case where such a Mn-Si deficient layer is not present. However, since the formation of these surface oxides is not completely suppressed in the annealing process, it is important to perform a proper secondary pickling after the annealing process in order to properly adhere the plating in the subsequent plating process.

[0056] Therefore, the combination of a winding temperature of 520°C or higher in the winding process and the secondary pickling described above in the secondary pickling process is important. Such a specific combination allows for sufficient or complete removal of Mn and / or Si-based surface oxides formed on the surface of the cold-rolled steel sheet during the annealing process. As a result, it becomes possible to form a plating layer of the desired thickness in the final plated steel sheet, in which the total concentration of at least one of Zn and Mn is 60% by mass or more. For example, if the hydrochloric acid aqueous solution contains an inhibitor, or if the hydrochloric acid concentration of the hydrochloric acid aqueous solution is less than 3%, or if the immersion temperature is less than 50°C, and / or the immersion time is less than 2 seconds, the Mn and / or Si-based surface oxides formed on the surface of the cold-rolled steel sheet during the annealing process cannot be sufficiently removed, and the adhesion of the plating is inhibited in the subsequent plating process due to these surface oxides. As a result, the plating cannot be properly adhered, and it becomes impossible to form the desired thickness of the plating layer in the final plated steel sheet. Preferably, the hydrochloric acid concentration of the hydrochloric acid aqueous solution is 4-8%, the immersion temperature is 70-90°C, and the immersion time is 4-50 seconds.

[0057] In the secondary pickling process, rinsing after the secondary pickling is also extremely important. For example, if the electrical conductivity of the rinsing solution used in rinsing is relatively high, more specifically higher than 40 mS / m, iron oxides may form on the surface of the cold-rolled steel sheet during rinsing after secondary pickling. If such iron oxides are present on the surface of the cold-rolled steel sheet, the adhesion of the plating in the subsequent plating process will be inhibited, similar to the case of Mn and / or Si-based surface oxides. In this case, it will be impossible to form the plating layer of the desired thickness on the final plated steel sheet. In contrast, in this manufacturing method, by performing the rinsing after secondary pickling with a rinsing solution having an electrical conductivity of 40 mS / m or less, the formation of iron oxides during rinsing after secondary pickling can be significantly suppressed, making it possible to properly adhere the plating in the subsequent plating process.

[0058] In a steel sheet containing three elements of Ni, Cu, and Sn simultaneously, the presence of these elements in the steel sheet promotes the formation of iron oxide during water washing after secondary pickling in addition to the formation of Mn- and / or Si-based surface oxides in the annealing process. Therefore, in a steel sheet containing three elements of Ni, Cu, and Sn simultaneously, it is extremely difficult to suppress the formation of these oxides and appropriately attach plating in the subsequent plating process. Thus, the fact that the formation of these oxides can be significantly suppressed by combining a Mn-Si deficiency layer formed with a predetermined thickness, i.e., a thickness of 0.3 μm or more, due to appropriate control of the coiling temperature in the coiling process, and specific secondary pickling and water washing in the secondary pickling process, is extremely unexpected and surprising. From the perspective of further suppressing the formation of iron oxide, the lower the electrical conductivity of the water washing solution, the more preferable it is. Specifically, it is preferably 25 mS / m or less, and more preferably 15 mS / m or less.

[0059] [Plating process] Next, in the plating process, plating is applied to at least one, preferably both surfaces of the cold-rolled steel sheet (base metal steel sheet). The plating process can be carried out by any suitable plating treatment effective to achieve the desired thickness of a plating layer with a total concentration of at least one of Zn and Mn of 60% by mass or more, such as electroplating, vapor deposition plating method, spraying or cold spraying method. Preferably, the plating process is carried out by electroplating. Electroplating can be carried out using a bath containing at least one of Zn and Mn and optionally added elements at a predetermined concentration, under the conditions of a current density of 5 - 20 A / dm 2 and an energization time of 2.0 - 20.0 seconds. Preferably, the current density is 8 - 15 A / dm 2 and the energization time is 3.0 - 10.0 seconds.

[0060] In this manufacturing method, in order to properly adhere the plating, it is important to carry out the plating process after thoroughly or completely removing Mn and / or Si-based surface oxides and iron oxides from the surface of the base steel sheet in the secondary pickling process; in other words, it is important to carry out the plating process after the secondary pickling process. Conversely, as long as the plating process is carried out after the secondary pickling process, carrying out the plating process before the secondary pickling process is not necessarily excluded. For example, by dividing the plating process into two steps, first performing the first plating treatment before the secondary pickling process, and then performing the second plating treatment after the secondary pickling process, it is possible to form a plating layer of the desired thickness in which the total concentration of at least one of Zn and Mn is 60% by mass or more. Alternatively, it is also possible to perform another plating treatment before the secondary pickling process and then carry out the plating process according to this manufacturing method after the secondary pickling process.

[0061] According to this manufacturing method, in steel sheets where coating adhesion is difficult to improve due to the simultaneous presence of three elements, Ni, Cu, and Sn, it becomes possible to sufficiently or completely remove Mn and / or Si-based surface oxides and iron oxides from the surface of the base steel sheet by combining a Mn-Si deficient layer formed to a predetermined thickness, i.e., 0.3 μm or more, due to appropriate control of the winding temperature in the winding process, with specific secondary pickling and water washing in the secondary pickling process. In connection with this, by carrying out an appropriate subsequent plating process, it is possible to manufacture plated steel sheets in which the thickness of the plating layer is controlled to less than 0.10 to 1.00 μm, with a total concentration of at least one of Zn and Mn being 60% by mass or more, as measured by EPMA. As mentioned above, Zn and Mn function as anodes during chemical conversion treatment and improve the chemical conversion treatmentability of the steel sheet by dissolving themselves. Therefore, plated steel sheets manufactured according to this manufacturing method promote the anode dissolution (etching) of Zn and / or Mn in the plating layer during the chemical conversion treatment, allowing for the uniform formation of a chemical conversion coating across the entire steel sheet. As a result, the adhesion of the coating is significantly improved. Consequently, plated steel sheets manufactured by this method achieve superior corrosion resistance compared to conventional plated steel sheets containing Ni, Cu, and Sn simultaneously. This allows for extended lifespan in the use of plated steel sheets for automobiles and building materials, contributing to industrial development.

[0062] The plated steel sheet according to the embodiment of the present invention can be used as various automobile parts as described above, for example, after a chemical conversion coating or paint film is optionally formed on its surface. Whether or not an automobile part having a paint film or chemical conversion coating includes the plated steel sheet according to the embodiment of the present invention can be determined by removing the paint film or chemical conversion coating from a sample taken from the automobile part. The sample collection location, paint film removal process, and chemical conversion coating removal process in this case are as follows.

[0063] [Sample collection location] When collecting samples from automotive parts, avoid the following locations (i) to (iv). (i) Within 20 mm of the toe of a spot weld, and within 20 mm of the toe of the bead of an arc / laser weld. (ii) Machining area with a radius of curvature of less than 15 mm, and areas within 5 mm of said machining area (iii) Ends within 5 mm from the cut end face of the part (iv) Areas within 5 mm of the area where red rust is visible to the naked eye

[0064] [Paint film removal process] For a sample cut from the automobile body, the paint film is removed under the following conditions to expose the steel plate. A paint remover (Neoriver #160, manufactured by Sansai Chemical Co., Ltd.) is applied to the surface at room temperature and left to stand for about 5 minutes. Then, the paint film is removed by rubbing with a hard sponge or the like (e.g., Kanefeel, manufactured by AION Co., Ltd.). After that, it is washed with water and dried. At this time, the remaining state of the paint film is confirmed by SEM-EPMA measurement of the sample surface (100 μm square, 5 fields of view) after washing with water and drying. In the elemental distribution image obtained by EPMA, regions with a C concentration of 10 mass% or more are identified, and if the area ratio of these regions is 5% or more, it is judged that the paint film has not been removed sufficiently. To measure the area ratio of regions with a C concentration of 10 mass% or more, first, an elemental distribution image of C is obtained in EPMA with the C concentration range set to 10-30%. The specific measurement conditions for EPMA are as follows. Equipment: JEOL Ltd. JXA-8230 Electron Probe Microanalyzer Acceleration voltage: 15kV Irradiation current: 0.05μA Surface analysis:WDS Analysis interval: 300 μm or longer Area ratio: Average value of 5 fields of view Next, the area fraction is measured by image processing of the obtained elemental distribution image. The image analysis software "ImageJ" is used for image processing. After loading the elemental distribution image of C into ImageJ, the image is binarized using "Make Binary" in "Process" > "Binary" so that areas with a C concentration of 10 mass% or more are displayed in black and areas with a C concentration of less than 10 mass% are displayed in white. After binarization, the value of "Area fraction" in "Results" is read using "Measure" in "Analyze" and this value is determined as the area fraction of the areas with a C concentration of 10 mass% or more. If the paint film is not sufficiently removed, the removal of the paint film is repeated until the area fraction of the areas with a C concentration of 10 mass% or more is less than 5%.

[0065] [Removal of chemical conversion coating] For samples cut from the automobile body and with the paint film removed, if the chemical conversion coating is, for example, a zinc phosphate coating, the chemical conversion coating is removed in accordance with JIS K 3151:1996. Specifically, the chemical conversion coating is removed by immersion in a 5% chromic acid aqueous solution heated to 75°C for 15 minutes. After that, it is washed with water and dried. At this time, the remaining state of the chemical conversion crystals is confirmed by SEM-EPMA measurement of the sample surface (100 μm square, 5 fields of view) after washing with water and drying. In the elemental distribution image obtained by EPMA, regions where the P concentration is 5% by mass or more are identified, and if the area ratio of the region is 5% or more, it is judged that the chemical conversion coating has not been removed sufficiently. To measure the area ratio of regions where the P concentration is 5% by mass or more, first, an elemental distribution image of P is obtained in EPMA with the P concentration range set to 5-10%. Then, the area ratio is measured by image processing of the obtained elemental distribution image. Image processing is performed using the image analysis software "ImageJ". After loading the elemental distribution image of P into ImageJ, the image is binarized using "Make Binary" in "Process" > "Binary" so that areas with a P concentration of 5 mass% or more are displayed in black and areas with a P concentration of less than 5 mass% are displayed in white. After binarization, the value of "Area fraction" in "Results" is read using "Measure" in "Analyze" and this value is determined as the area percentage of areas with a P concentration of 5 mass% or more. If the chemical conversion coating is not sufficiently removed, the removal of the chemical conversion coating is repeated until the area percentage of areas with a P concentration of 5 mass% or more is less than 5%.

[0066] The present invention will be described in more detail below with reference to examples, but these examples are merely examples of the present invention, and the present invention is not limited in any way to these examples. Needless to say, the present invention can be modified as desired without departing from the spirit of the invention. [Examples]

[0067] In the following embodiments, plated steel sheets according to the present invention were manufactured under various conditions, and the properties of the manufactured plated steel sheets were investigated.

[0068] First, molten steel was cast using a continuous casting method to form steel billets having the chemical composition shown in Table 1. After the steel billets were cooled, they were reheated to 1200°C and hot-rolled, and then wound at the winding temperatures shown in Table 2. Hot rolling was carried out by rough rolling and finish rolling, with the finish rolling ending at 900-1050°C and a reduction ratio of 30%. Next, the obtained hot-rolled steel sheets were subjected to primary pickling, and then cold-rolled at a reduction ratio of 50% to obtain cold-rolled steel sheets with a thickness of 1.6 mm. Next, the obtained cold-rolled steel sheets were subjected to an annealing process in which they were heated to a temperature of 800°C in an atmosphere with an oxygen concentration of 20 ppm or less, a dew point of 0°C, and 4% hydrogen (nitrogen balance), and held for 100 seconds.

[0069] Next, the annealed cold-rolled steel sheets underwent secondary pickling. Specifically, the secondary pickling was carried out by immersing the cold-rolled steel sheets in an aqueous solution with a 5% hydrochloric acid concentration that did not contain inhibitors at a temperature of 80°C for 4.5 seconds, and then washing the cold-rolled steel sheets with a washing solution having the electrical conductivity shown in Table 2. Finally, the resulting base steel sheets were subjected to a current density of 10 A / dm² using a bath containing metal species such as Zn and Mn at predetermined concentrations. 2 Furthermore, electroplating was performed under conditions of energizing time of 5.0 seconds to obtain plated steel sheets in which a plating layer containing the metal species shown in Table 2 was attached to both sides of the base steel sheet. The "thickness of the plating layer" in Table 2 indicates the thickness of the plating layer in which the total concentration of at least one of Zn and Mn is 60% by mass or more when the cross-section of the plated steel sheet is measured by EPMA.

[0070] [Table 1]

[0071] [Table 2]

[0072] The properties of the obtained plated steel sheets were measured and evaluated by the following method.

[0073] [Evaluation of coating adhesion] The adhesion of the coating film was evaluated as follows. First, a 50mm x 50mm sample of the plated steel sheet manufactured above was subjected to zinc phosphate treatment as a chemical conversion treatment under the following conditions. Degreasing: Immerse in a degreasing agent (Fine Cleaner E2083) at 40°C for 2 minutes, then rinse with water. Surface preparation: Immerse in a surface preparation agent (Preparen Z) at room temperature for 30 seconds. Chemical treatment: Immerse in zinc phosphate treatment agent (Palbond L3020) at 40°C for 2 minutes, then rinse with water and dry.

[0074] For samples of plated steel sheets that had undergone chemical conversion treatment, electrodeposition coating (Powernix Excel 1200: manufactured by Nippon Paint Industrial Coating Co., Ltd.) was performed at an electrodeposition temperature of 30°C and a film thickness of 18 μm, followed by a baking treatment at 170°C for 30 minutes. Next, a salt water immersion test (SDT) was performed on the electrodeposited samples. Specifically, the electrodeposited samples were immersed in a 5% NaCl aqueous solution at 50°C for 1000 hours. After the SDT test, the removed samples were dried, and then a tape peel test was performed on one side of the sample. The peeled tape was scanned, and the area percentage of the coating that had peeled off was calculated by binarization using the image analysis software "ImageJ". The coating adhesion was evaluated as follows. AAA: Peeling area ratio less than 5% AA: Peeling area ratio less than 5-10% A: Peeling area ratio 10-15% B: Peeling area rate over 15%

[0075] Plated steel sheets containing Ni, Cu, and Sn were evaluated as having improved coating adhesion when the coating adhesion rating was AAA, AA, or A. The results are shown in Table 2.

[0076] Referring to Table 2, in Comparative Example 23, the low winding temperature resulted in insufficient formation of the internal oxide layer, which prevented the formation of a Mn-Si deficient layer with a thickness of 0.3 μm or more. As a result, the thickness of the plating layer, in which the combined concentration of at least one of Zn and Mn was 60% by mass or more, was less than 0.10 μm, leading to reduced coating adhesion. In Comparative Example 25, in addition to the low winding temperature, the high electrical conductivity of the rinsing solution used for rinsing after secondary pickling prevented sufficient suppression of the formation of Mn and / or Si-based surface oxides during the annealing process, and furthermore, the formation of iron oxides during rinsing after secondary pickling was also not sufficiently suppressed. As a result, the thickness of the plating layer was less than 0.10 μm, leading to reduced coating adhesion. In Comparative Examples 24 and 26, the high electrical conductivity of the rinsing solution used for rinsing after secondary pickling prevented sufficient suppression of the formation of iron oxides during rinsing after secondary pickling. As a result, the thickness of the plating layer became less than 0.10 μm, and the adhesion of the coating film decreased. In Comparative Example 27, the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn was 60% by mass or more, was too thick, which is thought to have reduced the amount of Fe dissolved from the base steel sheet during the chemical conversion treatment, thus lowering the P ratio of the chemical conversion treated film. As a result, the adhesion of the coating film decreased.

[0077] In contrast, in all the examples, the coating adhesion of the plated steel sheets was significantly improved by applying plating such that the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn was 60% by mass or more as measured by EPMA, was controlled to less than 0.10 to 1.00 μm. In particular, in Examples 2, 3, 8, 9, 14, 15, and 20, in which the thickness of the plating layer was 0.30 μm or more, the coating adhesion was evaluated as AA, indicating further improvement in coating adhesion. In Examples 4 to 6, 10 to 12, 16 to 18, 21, and 22, in which the thickness of the plating layer was 0.50 μm or more, the coating adhesion was evaluated as AAA, indicating further improvement in coating adhesion.

Claims

1. A plated steel sheet comprising a base steel sheet and a plating layer disposed on the surface of the base steel sheet, The aforementioned base steel plate is, by mass%, Ni: 0.010-1.000%, Cu: 0.010 to 1.000%, and It has a chemical composition containing Sn: 0.003 to 1.000%, In the elemental distribution image obtained by measuring the cross-section of the plated steel sheet with EPMA, The thickness of the plating layer is 0.10 to less than 1.00 μm, and the total concentration of at least one of Zn and Mn is 60% by mass or more. The thickness of a plating layer in which the total concentration of at least one element, Zn and Mn, is 60% by mass or more is determined by taking five samples from the surface of a plated steel sheet, defining one field of view as a rectangular area of ​​80 μm in the thickness direction and 100 μm in the direction perpendicular to the thickness direction, and imaging five fields of view in total for the five samples using an EPMA under conditions of acceleration voltage: 15 kV and irradiation current: 5 × 10⁻⁷ A at a magnification of 1000x, determining the region in the surface portion of the plated steel sheet in which the total concentration of at least one element, Zn and Mn, is 60% by mass or more from the elemental distribution image obtained, determining the value obtained by dividing the area of ​​the region by the length of the field of view perpendicular to the thickness direction (100 μm) as the thickness of the plating layer in one sample, and calculating the average of the thicknesses obtained for the five samples.

2. The plated steel sheet according to claim 1, characterized in that the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn is 60% by mass or more, is 0.30 to less than 1.00 μm.

3. The plated steel sheet according to claim 2, characterized in that the thickness of the plating layer, in which the total concentration of at least one of Zn and Mn is 60% by mass or more, is 0.50 to less than 1.00 μm.

4. The aforementioned chemical composition is, in mass%, Ni: 0.040-1.000%, Cu: 0.040 to 1.000%, and Sn: 0.004-1.000% A plated steel sheet according to any one of claims 1 to 3, characterized by including the following:

5. A plated steel sheet according to any one of claims 1 to 3, characterized by having a Vickers hardness of 200 Hv or more.

6. A component characterized by comprising a plated steel sheet according to any one of claims 1 to 3.

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