Title of the invention: Hot-dip galvanizing method, method for manufacturing alloyed hot-dip galvanized steel sheet using the hot-dip galvanizing method, method for manufacturing hot-dip galvanized steel sheet using the hot-dip galvanizing method, alloyed hot-dip zinc. Plated steel sheet and hot-dip galvanized steel sheet
Technical field
[0001]
　The present invention relates to a hot-dip galvanizing method, a method for producing an alloyed hot-dip galvanized steel sheet using the hot-dip galvanizing method, a method for producing a hot-dip galvanized steel sheet using the hot-dip galvanizing method, and an alloyed hot-dip galvanized steel sheet. The present invention relates to a plated steel sheet and a hot-dip galvanized steel sheet.
Background technology
[0002]
　The hot-dip galvanized steel sheet (hereinafter, also referred to as GI) and the alloyed hot-dip galvanized steel sheet (hereinafter, also referred to as GA) are manufactured by the following manufacturing methods. First, a steel sheet (base steel sheet) to be hot-dip galvanized is prepared. The base steel plate may be a hot-rolled steel plate or a cold-rolled steel plate. When the base steel sheet is a hot-rolled steel sheet, for example, a pickled hot-rolled steel sheet is prepared. If necessary, the pickled hot-rolled steel sheet may be subjected to a Ni pre-plating treatment to prepare a hot-rolled steel sheet having a Ni layer formed on its surface. A hot-rolled steel sheet that has been subjected to a treatment other than the above may be prepared as a base steel sheet. When the base steel sheet is a cold-rolled steel sheet, for example, an annealed cold-rolled steel sheet is prepared. If necessary, the annealed cold-rolled steel sheet may be subjected to a Ni pre-plating treatment to prepare a cold-rolled steel sheet having a Ni layer formed on its surface. A cold-rolled steel sheet subjected to a treatment other than the above may be prepared as a base steel sheet. The prepared base steel sheet (the above-mentioned hot-rolled steel sheet or cold-rolled steel sheet) is immersed in a hot-dip galvanized bath to perform a hot-dip galvanizing treatment to produce a hot-dip galvanized steel sheet. When the alloyed hot-dip galvanized steel sheet is manufactured, the alloyed hot-dip galvanized steel sheet is further manufactured by heat-treating the hot-dip galvanized steel sheet in an alloying furnace.
[0003]
　The details of the hot-dip galvanized treatment in the method for producing the hot-dip galvanized steel sheet and the alloyed hot-dip galvanized steel sheet are as follows. The hot-dip galvanizing equipment used for the hot-dip galvanizing treatment includes a hot-dip galvan pot containing a hot-dip galvanizing bath, a sink roll arranged in the hot-dip galvanizing bath, and a gas wiping device.
[0004]
　In the hot-dip galvanizing treatment, the steel sheet (base steel sheet) is immersed in a hot-dip galvanizing bath. Then, the sink roll arranged in the hot-dip galvanizing bath changes the traveling direction of the steel sheet upward, and pulls the steel sheet out of the hot-dip galvanizing bath. Wiping gas is sprayed from the gas wiping device onto the surface of the steel sheet that is pulled up and moves upward. The wiping gas scrapes off excess molten zinc and adjusts the amount of plating adhered to the surface of the steel sheet. The hot-dip galvanizing treatment is carried out by the above method. In the case of producing an alloyed hot-dip galvanized steel sheet, a steel sheet having an adjusted plating adhesion amount is further charged into an alloying furnace to carry out an alloying treatment.
[0005]
　In the hot-dip galvanizing treatment described above, Fe is eluted in the hot-dip galvanizing bath from the steel sheet immersed in the hot-dip galvanizing bath. When Fe eluted from the steel sheet in the hot-dip galvanizing bath reacts with Al and Zn existing in the hot-dip galvanizing bath, an intermetallic compound called dross is formed. There are top dross and bottom dross in dross. Top dross is an intermetallic compound having a lighter specific gravity than that of a hot-dip galvanizing bath, and is a dross that floats on the liquid surface of the hot-dip galvanizing bath. The bottom dross is an intermetallic compound having a heavier specific gravity than the hot-dip galvanizing bath, and is a dross deposited on the bottom of the hot-dip galvanized pot. Of these dross, in particular, the bottom dross is wound up from the bottom of the accumulated hot-dip galvanized pot by the accompanying flow generated by the progress of the steel sheet in the hot-dip galvanizing bath during the hot-dip galvanizing process. In this case, the bottom dross floats in the hot dip galvanizing bath. Such floating bottom dross may adhere to the surface of the steel sheet during the hot-dip galvanizing process. The bottom dross adhering to the surface of the steel sheet may cause punctate defects on the surface of the alloyed hot-dip galvanized steel sheet or the hot-dip galvanized steel sheet. Such surface defects caused by bottom dross are referred to as "dross defects" in the present specification. Dross defects deteriorate the appearance of alloyed hot-dip galvanized steel sheets and hot-dip galvanized steel sheets, and reduce corrosion resistance. Therefore, it is preferable that the occurrence of dross defects can be suppressed.
[0006]
　Techniques for suppressing the occurrence of dross defects have been proposed in Japanese Patent Application Laid-Open No. 11-35096 (Patent Document 1) and Japanese Patent Application Laid-Open No. 11-35097 (Patent Document 2).
[0007]
　In Patent Document 1, in the method for producing an alloyed hot-dip galvanized steel sheet, the hot-dip galvanized bath temperature is T (° C.), and the boundary Al concentration defined by Cz = −0.015 × T + 0.76 is Cz (wt%). And. In this case, the hot-dip zinc bath temperature T is kept in the range of 435 to 500 ° C., and the Al concentration in the bath is kept in the range of Cz ± 0.01 wt%.
[0008]
　Specifically, Patent Document 1 describes as follows. The composition of the dross changes depending on the Al concentration in the bath. Specifically, in a hot-dip zinc bath maintained at 465 ° C., when the Al concentration in the bath is 0.14% or more, the dross is Fe—Al type (top dross). If the bath Al concentration is lower than 0.14%, dross δ of Fe-Zn-based (bottom dross) 1 becomes phase. When the Al concentration in the bath becomes lower, the dross becomes the Fe—Zn system (bottom dross) ζ phase. The dross is [delta] 1 when causing phase transformation ζ phase from phase, and, [delta] from dross ζ phase 1 when causing phase transformation phase, the phase transformation, the dross is refinement. Therefore, in Patent Document 1, [delta] 1 to define the phase transformation boundaries in phase and ζ phase as a boundary Al concentration Cz. Then, the Al concentration in the bath is controlled at the boundary Al concentration Cz ± 0.01 wt%. In this case, bath Al concentration dross δ if it exceeds the boundaries Al concentration Cz 1 next phase, the dross becomes ζ phase if less than the boundary Al concentration Cz. By controlling the Al concentration in Cz ± 0.01 wt%, dross in the bath is [delta] 1 repeats the phase transformation between the phase and the ζ phase. Therefore, Patent Document 1 describes that the dross can be miniaturized and the occurrence of dross defects can be suppressed.
[0009]
　In Patent Document 2, in the method for producing an alloyed hot-dip galvanized steel sheet, the Al concentration in the bath is kept within the range of 0.15 ± 0.01 wt%. Specifically, Patent Document 2 describes as follows. In a bath Al concentration 0.15 wt% or more, dross Fe-Al phase (top dross), and the bath Al concentration below 0.15 wt%, dross [delta] 1 becomes phase. Dross Fe-Al phase and [delta] 1 is repeated with phase transformation in the phase, the phase transformation, the dross is refinement. Therefore, the Al concentration in the bath is kept within the range of 0.15 ± 0.01 wt%. As a result, the dross can be miniaturized, and as a result, the occurrence of dross defects can be suppressed, as described in Patent Document 2.
Prior art literature
Patent documents
[0010]
Patent Document 1: Japanese Patent Application Laid-Open No. 11-35096
Patent Document 2: Japanese Patent Application Laid-Open No. 11-35097
Non-patent literature
[0011]
Non-Patent Document 1: Practical Applications of Phase Diagrams in Continuus Galvanizing, Nai-Yong Tang, Journal of Phase Equilibria and Diffusion. 27 No. 5,2006
Outline of the invention
Problems to be solved by the invention
[0012]
Previous studies have reported that there are four types of dross 　that can occur in hot-dip galvanizing treatment: top dross, δ 1- phase dross, Γ 1- phase dross, and ζ-phase dross. In Patent Document 1, the hot-dip galvanizing treatment is operated so that the Al concentration in the bath is near the boundary between the δ 1- phase dross and the ζ-phase dross. As a result, the δ 1- phase dross, which is the main cause of dross defects, is miniaturized. In Patent Document 2, bath Al concentration top dross and [delta] 1 to operate so that the vicinity of the boundary between the phase dross. As a result, the δ 1- phase dross, which is the main cause of dross defects, is miniaturized.
[0013]
　However, even when the hot-dip galvanizing treatment is performed in the operation by the method proposed in Patent Document 1 and Patent Document 2, the surface of the alloyed hot-dip galvanized steel sheet or the hot-dip galvanized steel sheet is still exposed. Dross defects may still occur.
[0014]
　Furthermore, on the surface of hot-dip galvanized steel sheets or alloyed hot-dip galvanized steel sheets manufactured through hot-dip galvanizing treatment, in addition to dross defects, surface defects caused by non-plating and physical contact such as abrasions are also present. May be formed. Therefore, in the hot-dip galvanizing treatment, not only reduction of dross defects but also reduction of non-plating and reduction of surface defects are required.
[0015]
　An object of the present disclosure is a hot-dip galvanizing treatment method capable of suppressing the occurrence of surface defects such as dross defects, non-plating, and surface defects, and a method for producing an alloyed hot-dip galvanized steel sheet using the hot-dip galvanizing treatment method. It is an object of the present invention to provide a method for producing a hot-dip galvanized steel sheet using a hot-dip galvanizing method, an alloyed hot-dip galvanized steel sheet, and a hot-dip galvanized steel sheet.
Means to solve problems
[0016]
　Galvanizing treatment method according to the present disclosure,
　be used in the production method of galvanized steel sheet or galvannealed steel sheet, using the hot-dip galvanizing bath containing Al, a galvanizing treatment method,
　the When the free Fe concentration in the hot-dip galvanizing bath is defined as X (mass%) and the free Al concentration in the hot-dip galvanizing bath is defined as Y (mass%), the free Fe concentration in the hot-dip galvanizing bath is defined as Y (mass%). And a concentration holding step is provided in which the free Al concentration is in the range satisfying the formulas (1) to (4).
　Y ≦ 2.674X + 0.03719 (1)
　Y ≧ 0.2945X + 0.1066 (2)
　X <0.0488 (3)
　Y ≦ 0.139 (4)
[0017]
　Here, the free Fe concentration in the hot-dip galvanizing bath means the Fe concentration melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Fe concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Fe content contained in the dross (top dross and bottom dross) (that is,). It means the Fe concentration (in the liquid phase). Similarly, the free Al concentration in the hot-dip galvanizing bath means the Al concentration melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Al concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Al content contained in the dross (top dross and bottom dross) (that is,). It means the Al concentration (in the liquid phase).
[0018]
　The method for producing an alloyed hot-dip galvanized steel sheet according to the present disclosure includes
　a step of manufacturing a hot-dip galvanized steel sheet by carrying out the hot-dip galvanized steel sheet described above, and an
　alloying process on the hot-dip galvanized steel sheet. Then, it is provided with an alloying treatment step for producing an alloyed hot-dip galvanized steel sheet.
[0019]
　The method for producing a hot-dip galvanized steel sheet according to the present disclosure includes
　a hot-dip galvanizing treatment step in which the above-mentioned hot-dip galvanizing treatment method is carried out on the steel sheet to form a hot-dip galvanizing layer on the surface of the steel sheet.
[0020]
　The alloyed hot-dip galvanized steel sheet according to the present disclosure includes a
　steel sheet and
　an alloyed hot-dip galvanized layer formed on the steel sheet, and has
　a
　maximum diameter of less than 3 to 50 μm on the surface of the alloyed hot-dip galvanized layer . δ One- phase dross is 2.5 pieces / cm 2 or
　more, dross with the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less, and
　non-plating with the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less. is there.
[0021]
　The hot-dip galvanized steel sheet according to the present disclosure includes a
　steel sheet and
　a hot-dip galvanized layer formed on the steel sheet, and has 2 　δ 1- phase dross having
　a
maximum diameter of less than 3 to 50 μm on the surface of the hot-dip galvanized layer. .5 pieces / cm 2 or 　more, dross having a maximum diameter of 50 μm or more is 10 pieces / 10 m 2 or less, and 　non-plating having a maximum diameter of 50 μm or more is 10 pieces / 10 m 2 or less.

Effect of the invention
[0022]
　In the hot-dip galvanized treatment method according to the present disclosure, surface defects such as dross defects, non-plating, and surface defects can be suppressed on the surface of the alloyed hot-dip galvanized steel sheet or hot-dip galvanized steel sheet.
[0023]
　The method for producing an alloyed hot-dip galvanized steel sheet according to the present disclosure can produce an alloyed hot-dip galvanized steel sheet in which surface defects are suppressed. The method for producing a hot-dip galvanized steel sheet according to the present disclosure can produce a hot-dip galvanized steel sheet in which surface defects are suppressed.
[0024]
　In the alloyed hot-dip galvanized steel sheet and hot-dip galvanized steel sheet according to the present disclosure, dross defects and non-plating are suppressed.
A brief description of the drawing
[0025]
FIG. 1 is a functional block diagram showing an overall configuration of a hot-dip galvanized steel sheet and a hot-dip galvanized line facility used for manufacturing an alloyed hot-dip galvanized steel sheet and a hot-dip galvanized steel sheet.
FIG. 2 is a side view of the hot-dip galvanizing facility in FIG.
FIG. 3 is a side view of a hot-dip galvanizing facility having a configuration different from that of FIG.
FIG. 4 is a side view of a hot-dip galvanizing facility having a configuration different from that of FIGS. 2 and 3.
FIG. 5 is a functional block diagram showing an overall configuration of a hot-dip galvanizing line facility having a configuration different from that of FIG.
FIG. 6 is a flow chart showing an example of a concentration maintaining step of the hot-dip galvanizing treatment method of the present embodiment.
FIG. 7 is a schematic diagram for explaining a method of measuring the longest diameter of dross.
Mode for carrying out the invention
[0026]
　In the present specification, surface defects of hot-dip galvanized steel sheets or alloyed hot-dip galvanized steel sheets include dross defects, non-plating, and surface defects. Dross defects are defects that occur when dross adheres to the hot-dip galvanized layer. The dross defect is a defect formed by sticking the dross to a part of the hot-dip galvanized layer or the alloyed hot-dip galvanized layer. The appearance of the dross-attached portion, that is, the dross defect is different from the appearance of the dross-free portion.
[0027]
　Non-plating means a part of the surface of the steel sheet that is not plated in the hot-dip galvanized layer and the alloyed hot-dip galvanized layer. Non-plating is mainly formed by peeling the metal fume adhering to the surface of the steel sheet before the hot-dip galvanizing treatment from the surface after the hot-dip galvanizing treatment. Although non-plating may occur due to factors other than metal fume, the main factor of non-plating is metal fume.
[0028]
　A surface defect means a defect that occurs as a result of the physical contact of the surface of the steel sheet with the dross. Surface flaws are, for example, scratches.
[0029]
　The present inventors have investigated the causes of the above-mentioned surface defects (dross defects, non-plating, and surface defects) in hot-dip galvanized steel sheets or alloyed hot-dip galvanized steel sheets. As a result, the following findings were obtained.
[0030]
　[Factors that cause
　dross defects ] The causes of dross defects have been studied so far. Dross defects are caused by dross generated during hot-dip galvanizing. As mentioned above, in the conventional research, it has been reported that the following types of dross generated in the hot-dip galvanizing treatment exist.
　(A) Top dross
　(B) δ 1- phase dross
　(C) Γ 1- phase dross
　(D) ζ-phase dross
[0031]
　Top dross has a lighter specific gravity than hot-dip galvanized baths. Therefore, the top dross easily floats on the liquid surface of the hot-dip galvanizing bath. The crystal structure of top dross is orthorhombic. The chemical composition of top dross is 45% Al, 38% Fe and 17% Zn in mass%. Top dross floats on the bath surface and is easy to collect. Therefore, top dross is unlikely to be a cause of dross defects.
[0032]
　δ 1- phase dross, Γ 1- phase dross, and ζ-phase dross are called bottom dross. The bottom dross has a heavier specific gravity than the hot-dip galvanized bath. Therefore, the bottom dross tends to be deposited on the bottom of the hot-dip galvanized pot in which the hot-dip galvanizing bath is stored.
[0033]
The crystal structure of the 　δ 1- phase dross is hexagonal. The chemical composition of the δ 1- phase dross is 1% or less of Al, 9% or more of Fe, and 90% or more of Zn in mass%. The crystal structure of the Γ 1- phase dross is a face-centered cubic crystal. Gamma 1 Chemical composition of the phase dross, in mass%, and 20% Fe, consisting of about 80% Zn. The crystal structure of the ζ-phase dross is monoclinic. The chemical composition of the ζ phase is 1% or less of Al, about 6% Fe, and about 94% Zn in mass%.
[0034]
　In previous studies, there were many reports that the main cause of dross defects was δ 1- phase dross. In the above-mentioned Patent Documents 1 and 2, it seems that the δ 1- phase dross is considered to be one of the causes of the dross defect. Accordingly, the present inventors have also initially, [delta] 1 considered phase dross is the main cause of dross defects were investigated and studied. However, even when the occurrence of δ 1- phase dross was suppressed in the hot-dip galvanized treatment, dross defects may still occur on the surfaces of the alloyed hot-dip galvanized steel sheet and the hot-dip galvanized steel sheet.
[0035]
　Accordingly, the present inventors have causes of dross defects [delta] 1 rather than the phase dross was thought that the other dross. Therefore, the present inventors have re-analyzed the composition and crystal structure of the dross-deficient portion using the alloyed hot-dip galvanized steel sheet in which the dross defect is generated. The present inventors further analyzed the types of dross generated in the hot-dip galvanizing bath. As a result, the present inventors have obtained the following findings regarding the dross defect, which are different from the results of conventional studies.
[0036]
　First, the chemical composition of the dross defect portion on the surface of the alloyed hot-dip galvanized steel sheet was analyzed using EPMA (Electron Probe Micro Analyzer). Furthermore, the crystal structure of the dross defect portion was analyzed using a TEM (Transmission Electron Microscope: transmission electron microscope). As a result, the chemical composition of the dross defect portion was 2% Al, 8% Fe, and 90% Zn in mass%, and the crystal structure was face-centered cubic.
[0037]
The chemical composition of 　δ 1- phase dross (Al of 1% or less by mass, Fe of 9% or more, and Zn of 90% or more), which was considered to be the main cause of the conventional dross defect, is the above-mentioned dross defect portion. Similar to the chemical composition of. However, the crystal structure of the δ 1- phase dross is hexagonal, not the face-centered cubic identified in the dross defect portion. Therefore, the present inventors considered that the delta 1- phase dross, which was conventionally considered to be the main cause of the dross defect, is not actually the main cause of the dross defect.
[0038]
　Therefore, the present inventors have identified the dross that causes the dross defect. Among the dross (A) to (D) described above, the chemical composition of the top dross is significantly different from the chemical composition of the dross defect portion. Regarding Γ 1- phase dross, the crystal structure is the same face-centered cubic crystal as the dross defect portion, but the chemical composition (20% Fe by mass% and 80% Zn) is larger than the chemical composition of the dross defect portion. different. Regarding the ζ-phase dross, the chemical composition (Al of 1% or less in mass%, Fe of about 6%, and Zn of about 94%) is different from the chemical composition of the dross defect portion, and the crystal structure (monoclinic crystal) ) Is also different from the crystal structure (face-centered cubic crystal) of the dross defect part.
[0039]
　Based on the above examination results, the present inventors considered that the dross defect was not caused by the dross of (A) to (D) described above. Then, the present inventors considered that the dross defect may be caused by other types of dross other than the above (A) to (D).
[0040]
　Therefore, the present inventors further analyzed the dross in the hot-dip galvanizing bath. The above-mentioned EPMA and TEM were used for the analysis of dross. As a result, the present inventors have found that Γ two- phase dross exists as the dross generated in the hot-dip galvanizing bath .
[0041]
The chemical composition of the 　Γ two- phase dross is, in mass%, 2% Al, 8% Fe and 90% Zn, which is consistent with the chemical composition of the analyzed dross defect portion described above. Furthermore, the crystal structure of the Γ two- phase dross is a face-centered cubic crystal, which is consistent with the crystal structure of the dross defect portion. Therefore, the present inventors considered that the Γ two- phase dross may be the main cause of the dross defect. Then, gamma 2 specific gravity of phase dross is greater than the specific gravity of the molten zinc plating bath, gamma 2 phase dross was true dross which may deposit on the bottom of the molten zinc pot.
[0042]
　As mentioned above, the top dross has a lighter specific gravity than the hot-dip galvanized bath. Since the top dross floats on the liquid surface of the hot-dip galvanizing bath, it is easy to recover. Therefore, top dross is less likely to cause dross defects.
[0043]
　Therefore, the present inventors further investigated the Γ two- phase dross and the other dross (B) to (D). As a result, it was found that the dross defect is caused by the hard dross, and the soft dross is difficult to form the dross defect.
[0044]
　As a result of further studies by the present inventors, it was found that among the dross (B) to (D) and the Γ 2- phase dross, the Γ 2- phase dross is a hard dross. Furthermore, it was found that the δ 1- phase dross and the ζ-phase dross are softer than the Γ 2- phase dross, and therefore are less likely to cause dross defects.
[0045]
　Based on the above examination results, the present inventors have found that the main cause of dross defects generated on the surfaces of alloyed hot-dip galvanized steel sheets and hot-dip galvanized steel sheets to be hot-dip galvanized is δ 1- phase dross. Instead, I thought it was a Γ two- phase dross. Furthermore, the present inventors consider that the dross classified as bottom dross is one of Γ 2- phase dross, δ 1- phase dross, ζ-phase dross, and Γ 1- phase dross, but in the hot-dip galvanizing bath, Γ. It was found that the one- phase dross was almost nonexistent.
[0046]
　Therefore, the present inventors further investigated the Γ two- phase dross and the other dross (A) to (D). As a result, the following matters were found.
[0047]
　Dross defects are caused by dross with a large particle size. That is, a dross having a large particle size tends to form a dross defect, and a dross having a small particle size does not easily form a dross defect. Specifically, a coarse dross having a maximum diameter of 50 μm or more is a cause of dross defects. A dross having a longest diameter of less than 50 μm is unlikely to form a dross defect. Here, the "longest diameter" is the largest line segment (μm) among the line segments connecting any two points on the outer circumference of the dross (the interface between the dross and the matrix) in the field of view of tissue observation described later. Means.
[0048]
　As for the growth rates of the dross (A) to (D) and the Γ 2- phase dross, the Γ 2- phase dross is the fastest and the δ 1- phase dross is the slowest. Thus, gamma 2 phase dross [delta] 1 grows faster than phase dross, [delta] 1 gamma at a much earlier stage than phase dross 2 longest diameter of phase exceeds 50 [mu] m. On the other hand, even if the δ 1- phase dross is generated, the longest diameter of the δ 1- phase is likely to be maintained as fine as less than 50 μm, and it is difficult to form a dross defect. In addition, the δ 1- phase dross is softer than the Γ 2- phase dross. Therefore, even if the δ 1- phase dross becomes coarse, dross defects are unlikely to occur.
[0049]
　Based on the above examination results, the present inventors have previously reported many main causes of dross defects occurring on the surface of alloyed hot-dip galvanized steel sheets and the surface of hot-dip galvanized steel sheets to be subjected to hot-dip galvanized treatment. It was concluded that it was Γ 2- phase dross instead of the δ 1- phase dross that had been used .
[0050]
　The present inventors further obtained the following findings. The Γ two- phase dross and the δ one- phase dross undergo phase transformation with each other. That is, depending on the conditions of hot-dip galvanizing treatment, gamma 2 phase dross [delta] 1 or phase transformation phase dross, [delta] 1 phase dross gamma 2 or phase transformation phase dross. Therefore, the present inventors considered that if the amount of δ 1- phase dross in the hot-dip galvanizing bath increases, the amount of Γ 2- phase dross in the hot-dip galvanizing bath decreases due to phase transformation.
[0051]
　Based on the above findings, the present inventors adjusted the operating conditions of the hot-dip galvanizing treatment so as to intentionally increase the δ 1- phase dross, which was conventionally considered to be the main cause of dross defects and was the target of reduction. It was thought that this would reduce the Γ two- phase dross in the hot-dip galvanizing bath and suppress dross defects. Therefore, the present inventors further investigated the relationship between the phase transformation between the δ 1- phase dross and the Γ 2- phase dross and the free Fe concentration and the free Al concentration in the hot-dip galvanizing bath. As a result, when the free Fe concentration in the hot-dip galvanizing bath is defined as X (mass%) and the free Al concentration is defined as Y (mass%), the free Fe concentration X satisfies the formula (3) described later, and the free Al concentration is satisfied. Assuming that Y satisfies the formula (4) described later, if the following formula (1) is satisfied , the phase transformation from the Γ 2- phase dross to the δ 1- phase dross is promoted, and Γ 2 in the hot-dip galvanizing bath is promoted. It was found that the amount of phase dross was reduced, and as a result, dross defects could be suppressed.
　Y ≦ 2.674X + 0.03719 (1)
[0052]
　On the other hand, the growth rate of the ζ phase dross, gamma 2 although slower than the growth rate of the phase dross, [delta] 1 faster than the growth rate of the phase dross. Therefore, if the ζ-phase dross is also coarsened, a dross defect may be formed. However, similar to the relationship between Γ 2- phase dross and δ 1- phase dross, ζ-phase dross and δ 1- phase dross also undergo phase transformation with each other. That is, depending on the conditions of hot-dip galvanizing process, the phase dross ζ is [delta] 1 or phase transformation phase dross, [delta] 1 phase dross or phase transformation ζ phase dross. Thus, gamma 2 as with phase dross, the ζ phase dross [delta] 1 by phase transformation phase dross, [delta] 1 by increasing the phase dross amount, to reduce the ζ phase dross amount, the cause of dross defects further reduced The present inventors considered. Therefore, the present inventors investigated the relationship between the phase transformation between the δ 1- phase dross and the ζ-phase dross and the free Fe concentration and the free Al concentration in the hot-dip galvanizing bath. As a result, assuming that the free Fe concentration X satisfies the formula (3) described later and the free Al concentration Y satisfies the formula (4) described later, if the following formula (2) is satisfied, the ζ phase dross becomes δ. 1It was found that the phase transformation to phase dross is promoted, the ζ-phase dross in the hot-dip galvanizing bath is reduced, and as a result, dross defects can be suppressed.
　Y ≧ 0.2945X + 0.1066 (2)
[0053]
　As described above, in order to suppress dross defects, it is effective to keep the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath within the range satisfying the formulas (1) and (2). is there.
[0054]
　[Factors causing non-plating] The
　present inventors further investigated the factors causing non-plating. Adhesion of metal fume to the surface of the steel sheet is considered to be the main cause of non-plating. Here, the metal fume is dust generated by solidification of metal vapor evaporated from the liquid surface of the hot-dip galvanizing bath.
[0055]
　The metal fume is generated by the adhesion of metal vapor to a part of the hot-dip galvanizing line equipment such as the lower end of the snout. When the metal fume grows to a certain size, it falls from a part of the hot-dip galvanizing line equipment such as a snout to the surface of the passing steel sheet and adheres to the surface of the steel sheet. A plating layer is not formed on the surface of the steel sheet to which the metal fume is attached. As a result, non-plating occurs. Here, "non-plating" means that the steel sheet is plated after foreign matter such as metal fume adheres to the surface of the steel sheet, and the foreign matter such as metal fume is peeled off from the plated steel sheet to form a plating layer. The area where the surface of the steel sheet is exposed. The longest diameter of non-plating is the maximum line segment (μm) of any two line segments on the outer circumference of non-plating (the boundary between the region where the plating layer is formed and the region where the surface of the steel sheet is exposed). ) Means.
[0056]
　As described above, metal fume, which is the main cause of non-plating, is generated by the generation of metal vapor. Therefore, the generation of metal fume can be suppressed by adjusting the bath temperature of the hot-dip galvanizing bath. If the generation of metal fume can be suppressed, the generation of non-plating can be suppressed.
[0057]
　By the way, Fe in the hot-dip galvanizing bath is eluted from the steel sheet immersed in the hot-dip galvanizing bath. The free Fe concentration X in the hot-dip galvanizing bath shows a positive correlation with the bath temperature of the hot-dip galvanizing bath. Therefore, the present inventors considered that if the free Fe concentration X in the hot-dip galvanizing bath is suppressed, the generation of metal fume, which is the main cause of non-plating, can be suppressed. As a result of further examination, if the free Fe concentration in the hot-dip galvanizing bath satisfies the formula (3) while satisfying the formulas (1) and (2), the formation of the metal fume is suppressed, which is caused by the metal fume. The present inventors have found that the occurrence of non-plating can be suppressed.
　X <0.0488 (3)
[0058]
　[Factors that cause surface defects] The
　present inventors further investigated the factors that cause surface defects. Top dross is considered to be the cause of surface defects. Specifically, it is considered that surface defects are caused by the following mechanism. As mentioned above, the specific gravity of the top dross is lighter than the specific gravity of the hot-dip galvanizing bath. Therefore, the top dross floats on the liquid surface of the hot-dip galvanizing bath. However, when a large amount of top dross is generated, a part of the top dross is caught in the sink roll or the support roll in the hot-dip galvanizing bath. The top dross caught in the sink roll or support roll is pressed against the steel plate. As a result, surface defects are generated on the steel sheet. Alternatively, top dross crystallizes from the vicinity of the sink roll or support roll. The crystallized top dross is sandwiched between the sink roll and the steel plate. The top dross sandwiched between the sink roll and the steel sheet is pressed against the steel sheet. As a result, surface defects occur.
[0059]
　As described above, the present inventors considered that if a large amount of top dross is generated, surface defects are likely to occur due to the above mechanism. Therefore, the present inventors have investigated a method for reducing the amount of top dross in order to suppress the occurrence of surface defects. As a result, the present inventors have found the following findings.
[0060]
　Top dross undergoes phase transformation with each other with Γ 2- phase dross and δ 1- phase dross. Therefore, in order to reduce the top dross, gamma from the top dross 2 phase transformation to phase, and / or, [delta] from the top dross 1 to allow promote phase transformation to phase, free Fe in the molten zinc plating bath The concentration X and the free Al concentration Y may be adjusted. As a result of the investigation, the free Fe concentration X in the hot-dip galvanizing bath did not easily affect the phase transformation between the top dross and the Γ 2- phase dross and the δ 1- phase dross. On the other hand, it was found that the free Al concentration Y in the hot-dip galvanizing bath greatly affects the phase transformation between the top dross and the Γ 2- phase dross and the δ 1- phase dross. Specifically, when the free Al concentration Y in the hot-dip galvanizing bath was 0.140% or less, the phase transformation from top dross to Γ 2- phase dross and / or δ 1- phase dross was promoted. Therefore, ideally, the present inventors considered that the free Al concentration Y in the hot-dip galvanizing bath should be maintained at 0.140% or less.
[0061]
　However, in the actual operation of the hot-dip galvanizing treatment, there is a possibility that the free Al concentration Y varies by ± 0.001% at the maximum in the control of the free Al concentration in the hot-dip galvanizing bath. Therefore, the present inventors hold the upper limit of the free Al concentration Y in the hot-dip galvanizing bath at 0.139%, that is, if the free Al concentration Y in the hot-dip galvanizing bath satisfies the formula (4). It was found that the occurrence of surface defects can be suppressed.
　Y ≤ 0.139 (4)
[0062]
　As described above, the present inventors have set the free Fe concentration X (mass%) and the free Al concentration Y (mass%) of the hot-dip galvanizing bath during the hot-dip galvanizing treatment from the formulas (1) to (4). It has been found that dross defects, non-plating and surface defects can be effectively reduced in alloyed hot-dip galvanized steel sheets and hot-dip galvanized steel sheets if they are held so as to be satisfied.
[0063]
　The hot-dip galvanizing method of the present embodiment completed based on the above findings, the method for producing an alloyed hot-dip galvanized steel sheet using the hot-dip galvanizing method, and the hot-dip galvanized steel sheet using the hot-dip galvanizing method. The method, the alloyed hot-dip galvanized steel sheet, and the hot-dip galvanized steel sheet have the following configurations.
[0064]
　The hot-dip galvanizing treatment method of [1] is a hot-dip galvanizing treatment method
　using a hot-dip galvanizing bath containing Al, which is used in the method for producing a hot-dip galvanized steel sheet or an alloyed hot-dip galvanized steel sheet.
　When the free Fe concentration in the hot-dip galvanizing bath is defined as X (mass%) and the free Al concentration in the hot-dip galvanizing bath is defined as Y (mass%), the free Fe in the hot-dip galvanizing bath is defined as Y (mass%). A concentration holding step is provided in which the concentration and the free Al concentration are in the range satisfying the formulas (1) to (4).
　Y ≦ 2.674X + 0.03719 (1)
　Y ≧ 0.2945X + 0.1066 (2)
　X <0.0488 (3)
　Y ≦ 0.139 (4)
[0065]
　Here, the free Fe concentration in the hot-dip galvanizing bath means the Fe concentration melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Fe concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Fe content contained in the dross (top dross and bottom dross) (that is,). It means the Fe concentration (in the liquid phase). Similarly, the free Al concentration in the hot-dip galvanizing bath means the Al concentration melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Al concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Al content contained in the dross (top dross and bottom dross) (that is,). It means the Al concentration (in the liquid phase).
[0066]
　The above-mentioned hot-dip galvanized treatment method can suppress the occurrence of dross defects, non-plating and surface defects in the hot-dip galvanized steel sheet or the alloyed hot-dip galvanized steel sheet.
[0067]
　In the method for producing an alloyed hot-dip galvanized steel sheet of [2], the hot-dip galvanized steel sheet is
　subjected to the hot-dip galvanized treatment method according to [1] to form the hot-dip galvanized layer on the surface of the steel sheet. It includes a galvanizing treatment step and
　an alloying treatment step of producing an alloyed hot-dip galvanized steel sheet by performing an alloying treatment on the steel sheet having a hot-dip galvanized layer formed on the surface thereof.
[0068]
　In the method for producing an alloyed hot-dip galvanized steel sheet according to the present embodiment, the above-mentioned hot-dip galvanized treatment is carried out. Therefore, in the produced alloyed hot-dip galvanized steel sheet, it is possible to suppress the occurrence of dross defects, non-plating and surface defects.
[0069]
　As for the method for producing a hot-dip galvanized steel sheet of [3],
　the hot-dip galvanizing treatment of forming a hot-dip galvanized layer on the surface of the steel sheet by carrying out the hot-dip galvanizing treatment method according to [1] on the steel sheet. Have a process.
[0070]
　In the method for producing a hot-dip galvanized steel sheet according to the present embodiment, the above-mentioned hot-dip galvanized treatment is carried out. Therefore, in the manufactured hot-dip galvanized steel sheet, it is possible to suppress the occurrence of dross defects, non-plating and surface defects.
[0071]
　The alloyed hot-dip galvanized steel sheet of [4] includes a
　steel sheet and
　an alloyed hot-dip galvanized layer formed on the steel sheet, and has
　a
　maximum diameter of less than 3 to 50 μm on the surface of the alloyed hot-dip galvanized layer. Δ 1- phase dross is 2.5 pieces / cm 2 or
　more, dross with the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less, and
　non-plating with the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less. Is.
[0072]
　Here, the dross of "dross having the longest diameter of 50 μm or more" is any one or more of top dross, δ 1- phase dross, Γ 1- phase dross, ζ-phase dross, and Γ 2- phase dross. It is considered that Γ 1- phase dross is almost absent in the hot-dip galvanizing bath .
[0073]
　On the surface of the hot-dip galvanized phase of the alloyed hot-dip galvanized steel sheet according to the present embodiment, a large amount of δ 1- phase dross, which is fine particles, is present. On the other hand, the dross of the coarse particles is small, and the adhesion of the coarse metal fume is small. Therefore, dross defects and non-plating are less likely to occur.
[0074]
　The hot-dip galvanized steel sheet of [5] includes a
　steel sheet and
　a hot-dip galvanized layer formed on the steel sheet, and has 　a δ 1- phase dross having
　a
maximum diameter of less than 3 to 50 μm on the surface of the hot-dip galvanized layer. 　The dross having 2.5 pieces / cm 2 or more and the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less, and 　the non-plating having the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less.

[0075]
　Here, the dross of "dross having the longest diameter of 50 μm or more" is any one or more of top dross, δ 1- phase dross, Γ 1- phase dross, ζ-phase dross, and Γ 2- phase dross. It is considered that Γ 1- phase dross is almost absent in the hot-dip galvanizing bath .
[0076]
　On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheet according to the present embodiment, many δ 1- phase dross, which are fine particles, are present. On the other hand, the dross of the coarse particles is small, and the adhesion of the coarse metal fume is small. Therefore, dross defects and non-plating are less likely to occur.
[0077]
　Hereinafter, a hot-dip galvanized treatment method, a method for manufacturing an alloyed hot-dip galvanized steel sheet, and a method for manufacturing a hot-dip galvanized steel sheet according to the present embodiment will be described with reference to the drawings. In the present specification and the drawings, the configurations having substantially the same functions are designated by the same reference numerals and the description thereof will not be repeated.
[0078]
　[Structure of Hot-dip Galvanized Line Equipment]
　FIG. 1 is a functional block diagram showing an example of the overall configuration of a hot-dip galvanized steel sheet and a hot-dip galvanized steel sheet used for manufacturing a hot-dip galvanized steel sheet. With reference to FIG. 1, the hot-dip galvanizing line equipment 1 includes an annealing furnace 20, a hot-dip galvanizing equipment 10, and a tempering rolling mill (skin pass mill) 30.
[0079]
　The annealing furnace 20 includes one or more heating zones (not shown) and one or more cooling zones arranged downstream of the heating zones. In the annealing furnace 20, the steel sheet is supplied to the heating zone of the annealing furnace 20, and the steel sheet is annealed. The annealed steel sheet is cooled in the cooling zone and transported to the hot dip galvanizing facility 10. The hot-dip galvanizing facility 10 is located downstream of the annealing furnace 20. In the hot-dip galvanized equipment 10, a hot-dip galvanized steel sheet is subjected to a hot-dip galvanized treatment to produce an alloyed hot-dip galvanized steel sheet or a hot-dip galvanized steel sheet. The tempering rolling mill 30 is arranged downstream of the hot dip galvanizing facility 10. In the tempering rolling mill 30, the alloyed hot-dip galvanized steel sheet or the hot-dip galvanized steel sheet manufactured in the hot-dip galvanized facility 10 is lightly reduced as necessary to be lightly reduced to alloy the hot-dip galvanized steel sheet or the hot-dip galvanized steel sheet or the hot-dip galvanized steel sheet. Adjust the surface of the galvanized steel sheet.
[0080]
　[About Hot-dip Galvanizing Equipment 10]
　FIG. 2 is a side view of the hot-dip galvanizing equipment 10 in FIG. With reference to FIG. 2, the hot-dip galvanizing facility 10 includes a hot-dip galvanized pot 101, a sink roll 107, a support roll 113, a gas wiping device 109, and an alloying furnace 111.
[0081]
　The annealing furnace 20 located upstream of the hot-dip galvanizing facility 10 is shielded from the atmospheric atmosphere, and is maintained in a reducing atmosphere. As described above, the annealing furnace 20 heats the steel sheet S that is continuously conveyed in the heating zone. As a result, the surface of the steel sheet S is activated, and the mechanical properties of the steel sheet S are adjusted.
[0082]
　The downstream end of the annealing furnace 20, which corresponds to the exit side of the annealing furnace 20, has a space in which the turndown roll 201 is arranged. The downstream end of the annealing furnace 20 is connected to the upstream end of the snout 202. The downstream end of the snout 202 is immersed in the hot dip galvanizing bath 103. The inside of the snout 202 is shielded from the atmospheric atmosphere and is maintained in a reducing atmosphere.
[0083]
　The steel sheet S whose transport direction has been changed downward by the turndown roll 201 passes through the snout 202 and is continuously immersed in the hot-dip galvanizing bath 103 stored in the hot-dip zinc pot 101. A sink roll 107 is arranged inside the hot-dip zinc pot 101. The sink roll 107 has a rotation axis parallel to the width direction of the steel plate S. The axial width of the sink roll 107 is larger than the width of the steel plate S. The sink roll 107 comes into contact with the steel plate S and changes the traveling direction of the steel plate S to the upper side of the hot dip galvanizing equipment 10.
[0084]
　The support roll 113 is arranged in the hot dip galvanizing bath 103 and above the sink roll 107. The support roll 113 includes a pair of rolls. The pair of rolls of the support roll 113 has a rotation axis parallel to the width direction of the steel plate S. The support roll 113 supports the steel plate S to be conveyed upward with the steel plate S whose traveling direction is changed upward by the sink roll 107.
[0085]
　The gas wiping device 109 is arranged above the sink roll 107 and the support roll 113 and above the liquid level of the hot-dip galvanizing bath 103. The gas wiping device 109 includes a pair of gas injection devices. The pair of gas injection devices has gas injection nozzles that oppose each other. During the hot-dip galvanizing process, the steel plate S passes between the pair of gas injection nozzles of the gas wiping device 109. At this time, the pair of gas injection nozzles face the surface of the steel plate S. The gas wiping device 109 blows gas onto both surfaces of the steel sheet S pulled up from the hot-dip galvanizing bath 103. As a result, the gas wiping device 109 scrapes off a part of the hot-dip galvanizing adhering to both surfaces of the steel sheet S, and adjusts the amount of hot-dip galvanizing adhering to the surface of the steel sheet S.
[0086]
　The alloying furnace 111 is arranged above the gas wiping device 109. The alloying furnace 111 passes the steel plate S conveyed upward through the gas wiping device 109 through the inside, and performs the alloying treatment on the steel plate S. The alloying furnace 111 includes a heating zone, a tropical zone, and a cooling zone in this order from the entry side to the exit side of the steel sheet S. The heating zone is heated so that the temperature (plate temperature) of the steel plate S becomes substantially uniform. The tropical zone maintains the plate temperature of the steel plate S. At this time, the hot-dip galvanized layer formed on the surface of the steel sheet S is alloyed to become an alloyed hot-dip galvanized layer. The cooling zone cools the steel sheet S on which the alloyed hot-dip galvanized layer is formed. As described above, the alloying furnace 111 carries out the alloying treatment using the heating zone, the tropical zone, and the cooling zone. The alloying furnace 111 carries out the above-mentioned alloying treatment when producing an alloyed hot-dip galvanized steel sheet. On the other hand, when producing a hot-dip galvanized steel sheet, the alloying furnace 111 does not carry out the alloying treatment. In this case, the steel plate S passes through the non-operating alloying furnace 111. Here, "not operating" means, for example, a state in which the power supply is stopped (a state in which the alloying furnace 111 is not started) while the alloying furnace 111 is placed online. The steel plate S that has passed through the alloying furnace 111 is conveyed to the next process by the top roll 115.
[0087]
　When producing a hot-dip galvanized steel sheet, the alloying furnace 111 may be moved offline as shown in FIG. In this case, the steel plate S is conveyed to the next process by the top roll 115 without passing through the alloying furnace 111.
[0088]
　When the hot-dip galvanizing facility 10 is a facility dedicated to hot-dip galvanized steel sheets, the hot-dip galvanizing facility 10 does not have to include the alloying furnace 111 as shown in FIG.
[0089]
　[About Other Configuration Examples of
　Hot-dip Galvanizing Line Equipment 1 ] The hot-dip galvanizing line equipment 1 is not limited to the configuration shown in FIG. For example, when a Ni pre-plating process is performed on a steel sheet before hot-dip galvanizing to form a Ni layer on the steel sheet, Ni is placed between the annealing furnace 20 and the hot-dip galvanizing facility 10 as shown in FIG. The pre-plating equipment 40 may be arranged. The Ni pre-plating equipment 40 includes a Ni plating cell for storing a Ni plating bath. The Ni pre-plating process is carried out by an electroplating method. The hot-dip galvanizing line equipment 1 of FIGS. 1 and 5 includes an annealing furnace 20 and a tempering rolling mill 30. However, the hot dip galvanizing line equipment 1 does not have to include the annealing furnace 20. Further, the hot-dip galvanizing line equipment 1 does not have to be equipped with a tempering rolling mill 30. The hot-dip galvanizing line equipment 1 may be provided with at least the hot-dip galvanizing equipment 10. The annealing furnace 20 and the tempering rolling mill 30 may be arranged as needed. Further, the hot-dip galvanizing line equipment 1 may be provided with a pickling equipment for pickling the steel sheet upstream of the hot-dip galvanizing equipment 10, and equipment other than the annealing furnace 20 and the pickling equipment. May be provided. The hot-dip galvanizing line equipment 1 may be further provided with equipment other than the tempering rolling mill 30 downstream of the hot-dip galvanizing equipment 10.
[0090]
　[About the hot-dip galvanizing treatment method of this embodiment]
　[ About the hot-dip galvanizing line equipment to be used ] In the hot-dip galvanizing treatment method of
　this embodiment, the hot-dip galvanizing line equipment 1 is used. The hot-dip galvanizing line equipment 1 has, for example, the configurations shown in FIGS. 1 and 5. As described above, the hot-dip galvanizing line equipment 1 used in the hot-dip galvanizing treatment method of the present embodiment may be the equipment shown in FIGS. 1 and 5, and is further added to the equipment shown in FIGS. 1 and 5. Other configurations may be added. Further, as described above, the hot-dip galvanizing line equipment 1 does not have to be provided with the annealing furnace 20. Further, the hot-dip galvanizing line equipment 1 does not have to be equipped with a tempering rolling mill 30. The hot-dip galvanizing line equipment 1 may be provided with at least the hot-dip galvanizing equipment 10. A well-known hot-dip galvanizing line facility 1 having a configuration different from that of FIGS. 1 and 5 may be used.
[0091]
　[About the steel sheet to be hot-dip galvanized]
　The steel type and size (thickness, width, etc.) of the steel sheet (base steel sheet) used in the hot-dip galvanizing method of the present embodiment are not particularly limited. The steel sheet is an alloyed hot-dip galvanized steel sheet or a hot-dip galvanized steel sheet according to each mechanical property (for example, tensile strength, workability, etc.) required for the alloyed hot-dip galvanized steel sheet or hot-dip galvanized steel sheet to be manufactured. A known steel sheet applied to the above may be used. A steel sheet used for an automobile outer plate may be used as a steel sheet to be hot-dip galvanized.
[0092]
　The steel sheet (base steel sheet) to be subjected to the hot-dip galvanizing treatment of the present embodiment may be a hot-rolled steel sheet or a cold-rolled steel sheet. As the base steel plate, for example, the following steel plate is used.
　(A) Pickled hot
　-dip steel sheet (b) Hot -dip steel sheet that has been pickled and then subjected to Ni pre-plating treatment to form a Ni layer on the surface
　(c) Hot-dip galvanized cold- rolled steel sheet
　Cold-rolled steel sheets
　(a) to (d) above, in which a Ni layer is formed on the surface of the steel sheet (d) after being annealed and then subjected to a Ni pre-plating process, are used in the hot dip galvanizing process of the present embodiment. It is an example of a steel plate to be manufactured. The steel sheet used for the hot-dip galvanizing treatment of the present embodiment is not limited to the above (a) to (d). A hot-rolled steel sheet or a cold-rolled steel sheet that has been subjected to a treatment other than the above (a) to (d) may be used as a steel sheet to be hot-dip galvanized.
[0093]
　[About hot-dip galvanizing bath]
　The main component of the hot-dip galvanizing bath is Zn. The hot-dip galvanizing bath further contains Al and Fe in addition to Zn.
[0094]
　[Hot-dip galvanizing treatment method]
　The hot-dip galvanizing treatment method of the present embodiment includes a concentration holding step. In the concentration holding step, when the free Fe concentration in the hot-dip galvanizing bath is defined as X (mass%) and the free Al concentration in the hot-dip galvanizing bath is defined as Y (mass%), the hot-dip galvanizing bath is used. The free Fe concentration X and the free Al concentration Y are in the range satisfying the formulas (1) to (4).
　Y ≦ 2.674X + 0.03719 (1)
　Y ≧ 0.2945X + 0.1066 (2)
　X <0.0488 (3)
　Y ≦ 0.139 (4)
　Here, what is the free Fe concentration in the hot-dip galvanizing bath? , Means the concentration of Fe melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Fe concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Fe content contained in the dross (top dross and bottom dross) (that is,). It means the Fe concentration (in the liquid phase). Similarly, the free Al concentration in the hot-dip galvanizing bath means the Al concentration melted in the hot-dip galvanizing bath. That is, in the present specification, the "free Al concentration in the hot-dip galvanizing bath" is melted in the hot-dip galvanizing bath excluding the Al content contained in the dross (top dross and bottom dross) (that is,). It means the Al concentration (in the liquid phase). Hereinafter, equations (1) to (4) will be described in detail.
[0095]
　[About the formula (1)] The
　formula (1) means a boundary (phase transformation line) in which the Γ 2- phase dross undergoes a phase transformation into a δ 1- phase dross in a hot-dip galvanizing bath . If the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath satisfy the formula (1), the chemical composition of the hot-dip galvanizing bath is more likely to be generated in the δ 1- phase dross than in the Γ 2- phase dross. It has become. In this case, assuming that the free Fe concentration X satisfies the formula (3) and the free Al concentration Y satisfies the formula (4), the Γ 2- phase dross in the hot-dip galvanizing bath undergoes phase transformation to δ 1- phase dross. Cheap. Therefore, in the galvanizing bath, [delta] 1 increases phase dross quantity, [delta] 1 with an increase in phase dross amount, gamma 2 phase dross amount is reduced. As mentioned above, the growth rate of δ 1 phase is much slower than that of Γ 2 phase. Therefore, in the hot-dip galvanizing bath, δ 1The phase maintains a fine state with a maximum diameter of less than 50 μm. As a result, the dross having the longest diameter of 50 μm or more is reduced. Therefore, the occurrence of dross defects can be suppressed. Here, the dross of "dross having the longest diameter of 50 μm or more" is any one of top dross, δ 1- phase dross, Γ 1- phase dross, ζ-phase dross, and Γ 2- phase dross. It is considered that Γ 1- phase dross is almost absent in the hot-dip galvanizing bath .
[0096]
　[About the formula (2)] The
　formula (2) means a boundary (phase transformation line) in which the ζ phase dross undergoes a phase transformation into a δ 1 phase dross in a hot dip galvanizing bath . If the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath satisfy the formula (2), the chemical composition of the hot-dip galvanizing bath is more likely to be generated in the δ 1- phase dross than in the ζ-phase dross. It has become. In this case, assuming that the free Fe concentration X satisfies the formula (3) and the free Al concentration Y satisfies the formula (4), the ζ-phase dross in the hot-dip galvanizing bath is likely to undergo a phase transformation into a δ 1- phase dross. .. Therefore, in the galvanizing bath, [delta] 1 increases phase dross quantity, [delta] 1 with an increase in phase dross amount, phase dross amount ζ is reduced. As described above, [delta] 1 growth rate of phase is slower than the growth rate of the ζ phase. Therefore, in the hot-dip galvanizing bath, coarse dross having a maximum diameter of 50 μm or more is reduced. As a result, the occurrence of dross defects can be suppressed.
[0097]
　[About formula (3)]
　Formula (3) shows an acceptable range of free Fe concentration X (mass%) in the hot-dip galvanizing bath. The free Fe concentration X in the hot-dip galvanizing bath shows a positive correlation with the bath temperature of the hot-dip galvanizing bath. If the free Fe concentration X is 0.0488% or more, the bath temperature of the hot-dip galvanizing bath is too high. Therefore, metal vapor is generated, and metal fume is likely to be generated. In this case, as described above, non-plating is likely to occur. If the free Fe concentration X in the hot-dip galvanizing bath is less than 0.0488%, that is, if the free Fe concentration X satisfies the formula (3), the bath temperature of the hot-dip galvanizing bath is appropriate and the metal vapor is generated. Hard to occur. Therefore, the generation of coarse metal fume is suppressed. As a result, the occurrence of non-plating having a maximum diameter of 50 μm or more is suppressed.
[0098]
　The lower limit of the free Fe concentration X in the hot-dip galvanizing bath is 0.0290% based on the formulas (1) and (2). The preferable lower limit of the free Fe concentration X is 0.0370%. The preferable upper limit of the free Fe concentration X is 0.0480%.
[0099]
　[About the formula (4)] The
　formula (4) shows an acceptable range of the free Al concentration Y (mass%) in the hot-dip galvanizing bath. The free Al concentration Y in the hot-dip galvanizing bath is related to the amount of top dross, Γ 2- phase dross, and δ 1- phase dross produced. If the free Al concentration Y exceeds 0.140%, the Γ 2- phase dross and / or the δ 1- phase dross are likely to undergo phase transformation into top dross. In this case, gamma 2 phase dross amount and / or [delta] 1 phase dross amount is reduced, the top dross amount increases. As described above, if the amount of top dross is too large, the top dross may be caught between the sink roll and the steel plate, and surface defects may be generated. Therefore, in the present embodiment, the formation of top dross is suppressed in order to suppress the occurrence of surface defects. Ideally, the free Al concentration Y in the hot-dip galvanizing bath should be maintained at 0.140% or less. However, in the actual operation of the hot-dip galvanizing treatment, even if the free Al concentration Y is controlled, there is a possibility that a variation of ± 0.001% may occur at the maximum in the free Al concentration Y. Therefore, in the present embodiment, the upper limit of the free Al concentration Y in the hot-dip galvanizing bath is set to 0.139%.
[0100]
　From the viewpoint of suppressing the occurrence of surface defects, the lower limit of the free Al concentration Y is 0.115% based on the formulas (1) and (2).
[0101]
　In the present embodiment, the free Al concentration in the hot-dip galvanizing bath is adjusted so that the free Al concentration Y in the hot-dip galvanizing bath satisfies the formula (4). In this case, it is possible to suppress the occurrence of surface defects while suppressing the excessive generation of top dross.
[0102]
　The preferable lower limit of the free Al concentration Y in the hot-dip galvanizing bath is 0.120%, more preferably 0.134%.
[0103]
　[Method of controlling free Fe concentration X and free Al concentration Y in the
　concentration holding step ] In the concentration holding step, as described above, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath are subjected to the formulas (1) to The range satisfies the equation (4). In the concentration holding step, the holding method is not particularly limited as long as the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath can be kept in the above ranges.
[0104]
　In the concentration holding step, for example, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath are kept within the range satisfying the above formula by the following method.
[0105]
　FIG. 6 is a flow chart showing an example of the concentration holding step. With reference to FIG. 6, an example of the concentration holding step includes a sampling step (S1), a free Fe concentration and free Al concentration determining step (S2), and a concentration adjusting step (S3). In the sample collection step (S1), a sample is collected from the hot dip galvanizing bath. In the free Fe and free Al concentration determination step (S2), the free Fe concentration and the free Al concentration in the hot-dip galvanizing bath are determined from the collected sample. In the concentration adjusting step (S3), the free Fe concentration and the free Al concentration in the hot-dip galvanizing bath are adjusted based on the determined free Fe concentration and free Al concentration so as to satisfy the formulas (1) to (4). To do. Hereinafter, each step will be described in detail.
[0106]
　[Sample collection step (S1)] In the
　sample collection step (S1), a sample is collected from the hot-dip galvanizing bath. The sampling period (the period from one sample to the next) may or may not be constant. For example, samples may be taken hourly. The next sample may be taken 1 hour after the sample is taken, and the next sample may be taken 30 minutes later. The sampling period is not particularly limited.
[0107]
　The amount of sample taken from the hot-dip galvanizing bath is not particularly limited. As long as the free Fe concentration X and the free Al concentration Y can be measured, the sample collection amount is not particularly limited. The sampling amount is, for example, 100 to 400 g. The collected sample is cooled and solidified. For example, the collected sample is brought into contact with a metal at room temperature having high thermal conductivity, and the sample is rapidly cooled to room temperature to solidify. A metal at room temperature having high thermal conductivity is, for example, copper. The sample collected may be cooled and solidified by other methods.
[0108]
　The sampling position in the hot-dip galvanizing bath is not particularly limited. For example, when the hot-dip galvanizing bath 103 is divided into three equal parts in the depth direction with reference to FIGS. 2 to 4, a sample may be taken in the uppermost region D1 in the hot-dip galvanizing bath 103. Samples may be taken in the central region D2 of the hot dip galvanizing bath 103. Samples may be taken in the lowermost region D3 of the hot dip galvanizing bath 103.
[0109]
　As shown in FIGS. 2 to 4, in the hot-dip galvanizing bath 103, the direction parallel to the plate width direction of the steel plate S is defined as the width direction W. The depth direction of the hot-dip galvanizing bath 103 is defined as the depth direction D. The direction perpendicular to the width direction W and the depth direction D is defined as the length direction L. In this case, preferably, a sample is sampled over time from within a specific width range in the width direction W, a specific depth range in the depth direction D, and a specific length range in the length direction L. To collect. In short, a sample is taken over time from the same position (within a specific region) in the hot-dip galvanizing bath 103.
[0110]
　More preferably, a sample is taken from the hot-dip galvanizing bath 103 at a depth region D107 within the range from the upper end to the lower end of the sink roll 107. This is because there is a high possibility that dross defects and surface defects will occur due to the dross floating in the vicinity of the sink roll 107. Therefore, preferably, a sample is taken from within a specific region including region D107.
[0111]
　[Free Fe Concentration and Free Al Concentration Determination Step (S2)] In the
　Free Fe Concentration and Free Al Concentration Determining Step (S2), the free Fe concentration X and the free Al concentration in the hot-dip galvanizing bath 103 are used using the collected sample. Determine Y. The method for determining the free Fe concentration X and the free Al concentration Y is not particularly limited. For example, the free Fe concentration X (mass%) and the free Al concentration Y (mass%) are determined based on the Fe concentration and Al concentration obtained by inductively coupled plasma (ICP) emission spectroscopy.
[0112]
　Specifically, the Fe concentration and the Al concentration are obtained by ICP emission spectroscopy using a sample. The Fe concentration obtained by the ICP emission spectroscopic analysis method includes not only the Fe concentration in the hot-dip galvanizing bath (free Fe concentration) but also the Fe concentration in the dross. That is, the Fe concentration obtained by the ICP emission spectroscopic analysis method is the so-called total Fe concentration. Similarly, the Al concentration obtained by the above-mentioned ICP emission spectroscopic analysis method includes not only the Al concentration in the hot-dip galvanizing bath (free Al concentration) but also the Al concentration in the dross. That is, the Al concentration obtained by the ICP emission spectroscopic analysis method is the so-called total Al concentration. Therefore, the free Fe concentration X and the free Al concentration Y are determined using the obtained total Fe concentration and total Al concentration and a well-known Zn—Fe—Al ternary phase diagram.
[0113]
　The method for determining the free Fe concentration X and the free Al concentration Y is as follows. Prepare a Zn-Fe-Al ternary phase diagram at the bath temperature when the sample was taken. As described above, the Zn—Fe—Al ternary phase diagram is well known and is also disclosed in FIGS. 2 and 3 in Non-Patent Document 1. Non-Patent Document 1 is a well-known paper among researchers and developers of hot-dip galvanizing baths. On the Zn—Fe—Al ternary phase diagram, points specified from the total Fe concentration and the total Al concentration obtained by ICP emission spectroscopy are plotted. Then, a tie line (conjugate line) is drawn on the liquid phase line in the Zn—Fe—Al ternary system state diagram from the plotted points. The Fe concentration at the intersection of the liquid phase line and the tie line is defined as the free Fe concentration (mass%), and the Al concentration at the intersection of the liquid phase line and the tie line is defined as the free Al concentration (mass%).
[0114]
　By the above method, the free Fe concentration X in the hot-dip galvanizing bath and the free Al concentration Y in the hot-dip galvanizing bath can be obtained. Of the chemical composition of the hot-dip galvanizing bath, the rest other than the free Fe concentration X and the free Al concentration Y can be regarded as Zn.
[0115]
　[Concentration Adjusting Step (S3)] In the
　concentration adjusting step (S3), in the hot-dip galvanizing bath based on the free Fe concentration X and the free Al concentration Y obtained in the free Fe concentration and the free Al concentration determining step (S2). The free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath are adjusted so that the free Fe concentration X and the free Al concentration Y satisfy the formulas (1) to (4). The adjustment method is not particularly limited as long as the free Fe concentration X and the free Al concentration Y are adjusted so as to satisfy the formulas (1) to (4).
[0116]
　[Method of adjusting free Fe concentration
　in hot-dip galvanizing bath ] For example, when adjusting the free Fe concentration X in the hot-dip galvanizing bath, the following (I) and / or (II) are carried out.
　(I) Adjust the bath temperature of the hot-dip galvanizing bath.
　(II) Adjust the transport speed of the steel sheet in the hot-dip galvanizing facility.
[0117]
　Regarding (I), if the temperature of the hot-dip galvanizing bath is raised, the amount of Fe that melts from the steel sheet immersed in the hot-dip galvanizing bath increases. On the other hand, if the temperature of the hot-dip galvanizing bath is lowered, the amount of Fe that melts from the steel sheet immersed in the hot-dip galvanizing bath is reduced. Therefore, the free Fe concentration X in the hot-dip galvanizing bath can be adjusted by adjusting the bath temperature of the hot-dip galvanizing bath. The bath temperature of the hot-dip galvanizing bath and the free Fe concentration X have a positive correlation. Therefore, the bath temperature of the hot-dip galvanizing bath is adjusted according to the free Fe concentration X obtained in step S2. Thereby, the free Fe concentration X in the hot-dip galvanizing bath can be adjusted so that the free Fe concentration X satisfies the formulas (1) to (4).
[0118]
　Regarding (II) above, if the transport speed of the steel sheet in the hot-dip galvanizing facility is slowed down, the amount of the steel sheet passing through the hot-dip galvanizing bath per unit time is reduced. In this case, the amount of Fe dissolved in the hot-dip galvanizing bath from the steel sheet immersed in the hot-dip galvanizing bath is reduced. Therefore, the free Fe concentration X in the hot-dip galvanizing bath can be reduced. On the other hand, if the transport speed of the steel sheet is increased, the amount of the steel sheet passing through the hot-dip galvanizing bath per unit time increases. In this case, the amount of Fe dissolved in the hot-dip galvanizing bath from the steel sheet immersed in the hot-dip galvanizing bath increases. Therefore, the free Fe concentration X in the hot-dip galvanizing bath can be increased.
[0119]
　The free Fe concentration X in the hot-dip galvanizing bath may be adjusted according to the above (I) and may not be adjusted according to the above (II). The free Fe concentration X in the hot-dip galvanizing bath may be adjusted according to (II) without being adjusted according to (I) above. The free Fe concentration X in the hot-dip galvanizing bath may be adjusted according to the above (I) and (II). Further, the free Fe concentration X in the hot-dip galvanizing bath may be adjusted by a method other than the above (I) and (II).
[0120]
　[Method of adjusting free Al concentration in
　hot-dip galvanizing bath ] The free Al concentration Y in the hot-dip galvanizing bath is adjusted by adding Al to the hot-dip galvanizing bath, for example. Al is added, for example, by immersing the Al ingot in a hot dip galvanizing bath. Al may be added by a method other than dipping the Al ingot in a hot-dip galvanizing bath. When Al is added to the hot-dip galvanizing bath by immersing the Al ingot in the hot-dip galvanizing bath, the Al ingot is placed in the hot-dip galvanizing bath at an immersion rate that can suppress a rapid change in the temperature of the hot-dip galvanizing bath. Immerse. The method for adjusting the free Al concentration Y in the hot-dip galvanizing bath is not limited to the above method. A well-known method may be used for adjusting the free Al concentration Y in the hot-dip galvanizing bath.
[0121]
　The free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath may be adjusted by a method other than the above-mentioned method. The bath temperature of the hot-dip galvanizing bath and the free Fe concentration X have a positive correlation. Therefore, for example, the relationship between the bath temperature in the hot-dip galvanizing bath used and the free Fe concentration X is investigated in advance. Then, after the relationship between the bath temperature and the free Fe concentration X is found, the free Fe concentration X may be adjusted by monitoring and adjusting the bath temperature. In this case, the free Fe concentration X in the hot-dip galvanizing bath is determined based on the bath temperature without determining the free Fe concentration X in the hot-dip galvanizing bath using the sample collected from the hot-dip galvanizing bath. Can be done. However, even in this case, the free Al concentration Y in the hot-dip galvanizing bath is determined by using a sample.
[0122]
　When adjusting the operating conditions based on the formulas (1) and (2), whether to preferentially control the free Fe concentration X or the free Al concentration Y is determined in the manufacturing process of the alloyed hot-dip galvanized steel sheet. It may be appropriately determined according to the operating conditions of the above, or the operating conditions in the manufacturing process of the hot-dip galvanized steel sheet.
[0123]
　[About more preferable bath temperature
　of the hot-dip galvanizing bath] The temperature (bath temperature) of the hot-dip galvanizing bath in the above-mentioned hot-dip galvanizing treatment method is preferably 465 to 480 ° C. The dross undergoes phase transformation into top dross, Γ 2- phase dross, and δ 1- phase dross, depending on the temperature of the hot-dip galvanizing bath and the free Al concentration Y in the hot-dip galvanizing bath . Γ Two- phase dross is likely to be formed in the region where the bath temperature is low. δ 1- phase dross is likely to be generated in a region where the bath temperature is higher than the region where Γ 2- phase dross is generated. Incidentally, the top dross, gamma 2 generation region and δ of phase dross 1 Free Al concentration Y is likely to produce a higher region than generation region of the phase dross.
[0124]
　If the bath temperature of the molten zinc plating bath 465 ° C. or higher, gamma 2 also [delta] than phase dross 1 towards the phase dross is more easily generated, gamma 2 phase dross [delta] 1 tends to phase transformation phase dross. Therefore, the Γ 2- phase dross decreases, and the δ 1- phase dross tends to increase. On the other hand, when the bath temperature of the hot-dip galvanizing bath is 480 ° C. or lower, metal evaporation is further suppressed and metal fume generation is further suppressed. Therefore, the preferred bath temperature of the hot-dip galvanized bath is 465 to 480 ° C. A more preferable lower limit of the bath temperature of the hot-dip galvanizing bath is 470 ° C.
[0125]
　The variation in the bath temperature of the hot-dip galvanizing bath when the hot-dip galvanizing treatment method is carried out, that is, the bath temperature of the hot-dip galvanizing bath when the steel plate is immersed in the hot-dip galvanizing bath (passing plate). The variation is preferably within the range of ± 3.0 ° C. Here, the variation in the bath temperature of the hot-dip galvanizing bath means the bath temperature of the entire hot-dip galvanizing bath (that is, all directions of the width direction W, the depth direction D, and the length direction L in the hot-dip galvanizing bath). Means the difference between the maximum and minimum temperatures of. A more preferable variation in the bath temperature of the hot-dip galvanizing bath is in the range of ± 2.0 ° C., and more preferably in the range of ± 1.5 ° C.
[0126]
　The change in the bath temperature of the hot-dip galvanizing bath when the hot-dip galvanizing treatment method is carried out, that is, the time of the bath temperature of the hot-dip galvanizing bath when the steel plate is passed through the hot-dip galvanizing bath Changes are preferably controlled within 3.0 ° C./min. The bath temperature of the hot-dip galvanizing bath can be adjusted by using a heater (not shown) arranged on the outer wall of the hot-dip galvanized pot 101.
[0127]
　As described above, in the hot-dip galvanizing treatment method of the present embodiment, the free Fe concentration X and the free Al concentration Y of the hot-dip galvanizing bath are set while the steel sheet is passed (immersed) in the hot-dip galvanizing bath. The range satisfies the equations (1) to (4). As a result, in the alloyed hot-dip galvanized steel sheet (GA) or hot-dip galvanized steel sheet (GI) that has been hot-dip galvanized, the occurrence of dross defects, non-plating, and surface defects can be suppressed.
[0128]
　[Method for manufacturing alloyed hot-dip galvanized steel sheet]
　The hot-dip galvanized treatment method of the present embodiment described above can be applied to the method for manufacturing alloyed hot-dip galvanized steel sheet (GA).
[0129]
　The method for producing an alloyed hot-dip galvanized steel sheet according to the present embodiment includes a hot-dip galvanized treatment step and an alloying treatment step. In the hot-dip galvanizing treatment step, the hot-dip galvanizing treatment method described above is carried out on the steel sheet to form a hot-dip galvanizing layer on the surface of the steel sheet. On the other hand, in the alloying treatment, the alloying treatment is carried out using the alloying furnace 111 shown in FIG. 2 on the steel sheet in which the hot-dip galvanizing layer is formed on the surface by the hot-dip galvanizing treatment step. As the alloying treatment method, it is sufficient to apply a well-known method.
[0130]
　An alloyed hot-dip galvanized steel sheet can be manufactured by the above manufacturing process. In the alloyed hot-dip galvanized steel sheet of the present embodiment, the hot-dip galvanized treatment method of the present embodiment described above is adopted. That is, during the hot-dip galvanizing treatment, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath are set within the range of the formulas (1) to (4). Therefore, in the alloyed hot-dip galvanized steel sheet, the occurrence of dross defects, non-plating and surface defects is suppressed.
[0131]
　The method for producing an alloyed hot-dip galvanized steel sheet of the present embodiment may include a hot-dip galvanized treatment step and a manufacturing step other than the alloying treatment step. For example, the method for producing an alloyed hot-dip galvanized steel sheet of the present embodiment may include a temper rolling step of performing temper rolling using the temper rolling machine 30 shown in FIG. 1 after the alloying treatment step. .. In this case, the appearance quality of the surface of the alloyed hot-dip galvanized steel sheet can be further improved. Further, a manufacturing process other than the temper rolling process may be included.
[0132]
　[Structure of Alloyed Hot-dip Galvanized Steel Sheet (GA)]
　The alloyed hot-dip galvanized steel sheet produced by the method for producing an alloyed hot-dip galvanized steel sheet of the present embodiment includes a steel sheet and an alloyed hot-dip galvanized steel sheet. ..
[0133]
　[About
　steel plate] The steel type and size (plate thickness, plate width, etc.) of the steel plate (base steel plate) are not particularly limited. As the steel sheet, a known steel sheet may be used according to each mechanical property (for example, tensile strength, workability, etc.) required for the alloyed hot-dip galvanized steel sheet to be manufactured. A steel sheet used for an automobile outer panel may be used as a steel sheet to be alloyed and hot-dip galvanized.
[0134]
　[About the alloyed hot-dip galvanized layer] The
　alloyed hot-dip galvanized layer is formed on the steel sheet. The alloyed hot-dip galvanized layer may have a well-known structure. The preferable Fe content in the chemical composition of the alloyed hot-dip galvanized layer is 9.0 to 12.0%. In this case, weldability, slidability and powdering resistance are improved.
[0135]
　Further, on the surface of the alloyed hot-dip galvanized layer, δ 1- phase dross having a maximum diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more, and dross having a maximum diameter of 50 μm or more is 10 pieces / 10 m 2. The number of non-plated pieces having a maximum diameter of 50 μm or more is 10 pieces / 10 m 2 or less. Here, the dross of "dross having the longest diameter of 50 μm or more" is one or more of top dross, δ 1- phase dross, Γ 1- phase dross, ζ-phase dross, and Γ 2- phase dross. It is considered that Γ 1- phase dross is almost absent in the hot-dip galvanizing bath .
[0136]
　On the surface of the alloyed hot-dip galvanized layer, the number density of δ 1- phase dross with the longest diameter of less than 3 to 50 μm (pieces / cm 2 ), the number density of dross with the longest diameter of 50 μm or more (pieces / 10 m 2 ), and The number density (pieces / 10 m 2 ) of non-plated products having the longest diameter of 50 μm or more is determined by the following methods.
[0137]
First, the method for measuring the number density of 　the δ 1- phase dross is obtained by the following method. A sample is taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet. The size of the sample is not particularly limited as long as the observation field of view described later can be secured. Of the surface of the alloyed hot-dip galvanized layer of the collected sample, a rectangular region of 2 mm × 2 mm is defined as one visual field, and any 10 visual fields are set as measurement targets. Elemental analysis by EPMA and / or crystal structure analysis by TEM is performed at 100x for each field of view to identify delta 1 phase dross in the field of view . When performing crystal structure analysis by TEM, after specifying the position of the dross to be measured by EPMA in advance, the crystal structure analysis is performed by irradiating the specified position with an electron beam.
[0138]
　Further, the longest diameter of each specified δ 1- phase dross is measured, and the number of δ 1- phase dross having a longest diameter of less than 3 to 50 μm is determined. The number density of δ 1- phase dross (2 mm × 2 mm × 10) based on the total number of δ 1- phase dross with the longest diameter of less than 3 to 50 μm and the total area of ​​10 fields (2 mm × 2 mm × 10) identified in 10 fields of view. Piece / cm 2 ) is calculated.
[0139]
　The number density of dross having the longest diameter of 50 μm or more (pieces / 10 m 2 ) and the number density of non-plated pieces having the longest diameter of 50 μm or more (pieces / 10 m 2 ) are determined by the following methods. A sample is taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet. The size of the sample is not particularly limited as long as the observation field of view described later can be secured. Of the surface of the alloyed hot-dip galvanized layer of the collected sample, a rectangular region of 1 m × 1 m is defined as one visual field, and any 10 visual fields are set as measurement targets. Dross with a maximum diameter of 50 μm or more and non-plating with a maximum diameter of 50 μm or more can be visually observed. It should be noted that dross in which it is difficult to visually determine whether or not the longest diameter is 50 μm or more and non-plating are determined using a 100x optical microscope.
[0140]
　Here, the longest diameter of the dross including the δ 1- phase dross is obtained by the following method. With reference to FIG. 7, in each dross 100, the largest line segment LS among the line segment LS connecting any two points of the interface (that is, the outer circumference of the dross) 150 between the dross 100 and the matrix 200 is defined as the “longest diameter”. Is defined. The longest diameter can be obtained by using image processing on a photographic image in the observation field. In this specification, dross having a maximum diameter of less than 3 μm is excluded because it is difficult to confirm and there is almost no effect on dross defects and non-plating. The maximum diameter of non-plating is also defined by the same method as the maximum diameter of dross described above.
[0141]
　The total number of dross having the longest diameter of 50 μm or more specified in 10 fields of view is counted. Similarly, the total number of unplated having a maximum diameter of 50 μm or more specified in 10 fields of view is counted. Based on the total number of dross having the longest diameter of 50 μm or more and the total area of ​​10 fields of view (10 m 2 ), the number density of dross having the longest diameter of 50 μm or more (pieces / 10 m 2 ) is obtained. Further, based on the total number of non-plated products having the longest diameter of 50 μm or more and the total area of ​​10 fields of view (10 m 2 ), the number density of non-plated products having the longest diameter of 50 μm or more (pieces / 10 m 2 ) is obtained.
[0142]
　As described above, in the method for producing the alloyed hot-dip galvanized steel sheet of the present embodiment, the hot-dip galvanized treatment method of the present embodiment described above is adopted. Therefore, in the hot-dip galvanizing bath, the formation of coarse dross is suppressed by satisfying the formulas (1) to (4) and generating a large amount of fine δ 1- phase dross. As a result, on the surface of the alloyed hot-dip galvanized steel sheet of the produced hot-dip galvanized steel sheet, there are many fine δ 1- phase dross and few coarse dross. Specifically, the number density of δ 1- phase dross having the longest diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more, and the number density of dross having the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less. There are 10 pieces / 10 m 2 or less for non-plating with the longest diameter of 50 μm or more . Therefore, in the alloyed hot-dip galvanized steel sheet of the present embodiment, dross defects and non-plating are suppressed.
[0143]
　On the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheet of the present embodiment, the preferable lower limit of the number density of δ 1- phase dross having a maximum diameter of less than 3 to 50 μm is 5.0 pieces / cm 2 . It is more preferably 7.5 pieces / cm 2 , and even more preferably 10.0 pieces / cm 2 . The upper limit of the number density of the δ 1- phase dross having the longest diameter of less than 3 to 50 μm is not particularly limited, but is, for example, 50.0 pieces / cm 2 . The number density of the δ 1- phase dross is a value obtained by rounding off the second decimal place of the obtained value (that is, a numerical value having the first decimal place).
[0144]
　Further, the preferable upper limit of the number density of the dross having the longest diameter of 50 μm or more is 5 pieces / 10 m 2 , more preferably 2 pieces / 10 m 2 , and further preferably 1 piece / 10 m 2 . The preferred upper limit of the number density of non-plated pieces having the longest diameter of 50 μm or more is 5 pieces / 10 m 2 , more preferably 2 pieces / 10 m 2 , and further preferably 1 piece / 10 m 2 .
[0145]
　[Method for manufacturing hot-dip galvanized steel sheet] The
　hot-dip galvanized steel sheet (GI) manufacturing method described above can also be applied to the hot-dip galvanized steel sheet (GI) manufacturing method.
[0146]
　The method for producing a hot-dip galvanized steel sheet according to the present embodiment includes a hot-dip galvanized treatment step. In the hot-dip galvanizing treatment step, the hot-dip galvanizing treatment method described above is carried out on the steel sheet to form a hot-dip galvanizing layer on the surface of the steel sheet. In the method for producing a hot-dip galvanized steel sheet of the present embodiment, the above-mentioned hot-dip galvanized treatment method of the present embodiment is adopted. That is, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath are set within the range of the formulas (1) to (4). Therefore, in the hot-dip galvanized steel sheet, the occurrence of dross defects, non-plating and surface defects is suppressed.
[0147]
　The method for manufacturing a hot-dip galvanized steel sheet of the present embodiment may include a manufacturing step other than the hot-dip galvanizing treatment step. For example, the method for producing a hot-dip galvanized steel sheet of the present embodiment may include a temper rolling step in which temper rolling is performed using the temper rolling machine 30 shown in FIG. 1 after the hot-dip galvanizing treatment step. In this case, the appearance quality of the surface of the hot-dip galvanized steel sheet can be further improved. Further, a manufacturing process other than the temper rolling process may be included.
[0148]
　[Structure of Hot-Dip Galvanized Steel Sheet (GI)]
　The hot-dip galvanized steel sheet produced by the method for producing a hot-dip galvanized steel sheet of the present embodiment includes a hot-dip galvanized steel sheet and a hot-dip galvanized steel sheet.
[0149]
　[About
　steel sheet] The steel sheet is the same as the steel sheet in the above-mentioned alloyed hot-dip galvanized steel sheet. That is, the steel type and size (plate thickness, plate width, etc.) of the steel plate (base steel plate) are not particularly limited. As the steel sheet, a known steel sheet may be used according to each mechanical property required for the hot-dip galvanized steel sheet to be manufactured. A steel sheet used for an automobile outer plate may be used as a steel sheet to be hot-dip galvanized.
[0150]
　[About the hot-dip galvanized layer] The
　hot-dip galvanized layer is formed on a steel plate. The hot-dip galvanized layer may have a well-known structure. The preferred Fe content in the hot-dip galvanized layer is more than 0% to 3.0%. The preferable Al content in the hot-dip galvanized layer is more than 0% to 1.0%.
[0151]
　[Number of dross on the surface of the
　hot-dip galvanized layer ] On the surface of the hot-dip galvanized layer, the maximum diameter of δ 1- phase dross is 2.5 pieces / cm 2 or more and the longest diameter is 50 μm or more. The dross is 10 pieces / 10 m 2 or less, and the non-plating having the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less.
[0152]
The number density 　of fine δ 1- phase dross (pieces / cm 2 ), the number density of coarse dross (pieces / 10 m 2 ), and the number density of non-plated (pieces / 10 m 2 ) on the surface of the hot-dip galvanized layer are alloys. It can be obtained by the same method as the number density of fine δ 1- phase dross, the number density of coarse dross, and the number density of non-plated on the surface of the hot-dip galvanized layer .
[0153]
　As described above, in the method for producing a hot-dip galvanized steel sheet of the present embodiment, the above-mentioned hot-dip galvanized treatment method of the present embodiment is adopted. Therefore, the formation of coarse δ 1- phase dross is suppressed by generating a large amount of fine δ 1- phase dross in the bath . As a result, on the surface of the hot-dip galvanized layer of the manufactured hot-dip galvanized steel sheet, there is a large amount of fine δ 1- phase dross and a small amount of coarse dross. Specifically, the number density of δ 1- phase dross having the longest diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more, and the dross having the longest diameter of 50 μm or more is 10 pieces / 10 m 2 or less. The maximum number of non-plated pieces having a maximum diameter of 50 μm or more is 10 pieces / 10 m 2 or less. Therefore, in the alloyed hot-dip galvanized steel sheet of the present embodiment, dross defects and non-plating are suppressed.
[0154]
　On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheet of the present embodiment, the preferable lower limit of the number density of δ 1- phase dross having the longest diameter of less than 3 to 50 μm is 5.0 pieces / cm 2 , and more preferably 7. It is .5 pieces / cm 2 , and more preferably 10.0 pieces / cm 2 . The upper limit of the number density of the δ 1- phase dross having the longest diameter of less than 3 to 50 μm is not particularly limited, but is, for example, 50.0 pieces / cm 2 . The number density of the δ 1- phase dross is a value obtained by rounding off the second decimal place of the obtained value (that is, a numerical value having the first decimal place).
[0155]
　Further, the preferable upper limit of the number density of the dross having the longest diameter of 50 μm or more is 5 pieces / 10 m 2 , more preferably 2 pieces / 10 m 2 , and further preferably 1 piece / 10 m 2 . The preferred upper limit of the number density of non-plated pieces having the longest diameter of 50 μm or more is 5 pieces / 10 m 2 , more preferably 2 pieces / 10 m 2 , and further preferably 1 piece / 10 m 2 .
Example 1
[0156]
　Hereinafter, the effect of one aspect of the hot-dip galvanizing treatment method of the present embodiment will be described in more detail by way of examples, and the conditions in the example have been adopted in order to confirm the feasibility and effect of the present invention. This is an example of conditions. Therefore, the hot-dip galvanizing treatment method of the present embodiment is not limited to this one-condition example.
[0157]
　An alloyed hot-dip galvanized steel sheet was manufactured using a hot-dip galvanized facility having the same configuration as in FIG.
[0158]
　As the steel plate, a steel plate for automobile outer panels was used. The chemical composition of the steel sheet of each test number was the same. A hot-dip galvanizing bath having a free Fe concentration X (mass%) and a free Al concentration Y (mass%) shown in Table 1 was prepared for the steel sheet. A hot-dip galvanized steel sheet was produced by performing a hot-dip galvanizing treatment using the prepared hot-dip galvanized bath. The bath temperature (° C.) of the hot-dip galvanizing bath at each test number was as shown in Table 1.
[0159]
[table 1]

[0160]
　The free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath were determined by the following methods. Samples were taken from the hot dip galvanizing bath. The sampling position of the hot-dip galvanized bath sample of each test number was the same for all test numbers. The sampling position (specific region) was the central position in the depth direction D of the hot-dip galvanizing bath, and was set to predetermined positions in the width direction W and the length direction L (both test numbers are the same positions).
[0161]
　A 200 g sample was taken from the hot dip galvanized bath. The sample was cooled to room temperature and solidified. Using the solidified sample, the total Fe concentration and the total Al concentration were obtained by ICP emission spectroscopy. The free Fe concentration X and the free Al concentration Y were determined using the obtained total Fe concentration and total Al concentration and a well-known Zn—Fe—Al ternary phase diagram. Specifically, a Zn-Fe-Al ternary phase diagram at the bath temperature of each test number was prepared. The points specified from the total Fe concentration and the total Al concentration obtained by ICP emission spectroscopy were plotted on the Zn—Fe—Al ternary phase diagram. Then, a tie line (conjugated line) was drawn on the liquid phase line in the Zn—Fe—Al ternary system state diagram from the plotted points. The Fe concentration at the intersection of the liquidus line and the tie line was defined as the free Fe concentration X (mass%). The Al concentration at the intersection of the liquidus line and the tie line was defined as the free Al concentration Y (mass%).
[0162]
　The obtained free Fe concentration X (mass%) is shown in the “Free Fe concentration X” column in Table 1. The obtained free Al concentration Y (mass%) is shown in the “Free Al concentration Y” column in Table 1. The F1 value is shown in the "F1" column in Table 1. Here, F1 = 2.674X + 0.03719. That is, F1 corresponds to the right side of the equation (1). The F2 value is shown in the "F2" column in Table 1. Here, F2 = 0.2945X + 0.1066. That is, F2 corresponds to the right side of the equation (2).
[0163]
　"S (Satisfied)" in the "Formula (1)" column in Table 1 indicates that the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath having the corresponding test numbers satisfy the formula (1). means. In "NS (Not Satisfied)" in the "Formula (1)" column in Table 1, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath having the corresponding test numbers do not satisfy the formula (1). Means that. "S" in the "Formula (2)" column in Table 1 means that the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath of the corresponding test numbers satisfy the formula (2). “NS” means that the free Fe concentration X and the free Al concentration Y do not satisfy the formula (2). "S" in the "Formula (3)" column in Table 1 means that the free Fe concentration X in the hot-dip galvanizing bath of the corresponding test number satisfies the formula (3), and "NS" is It means that the free Fe concentration X does not satisfy the formula (3). "S" in the "Formula (4)" column in Table 1 means that the free Al concentration Y in the hot-dip galvanizing bath of the corresponding test number satisfies the formula (4), and "NS" is It means that the free Al concentration Y does not satisfy the formula (4).
[0164]
　The hot-dip galvanized steel sheet was alloyed using an alloying furnace to produce an alloyed hot-dip galvanized steel sheet. The heating temperature in the alloying treatment was constant (510 ° C.) in all of the test numbers.
[0165]
　[Evaluation test]
　[Dross number density measurement test on the surface of alloyed hot-dip galvanized layer]
　Number of δ 1- phase dross on the surface of alloyed hot-dip galvanized steel sheet of each manufactured test number The density was determined by the following method. A sample was taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet. Of the surface of the alloyed hot-dip galvanized layer of the sample, a rectangular region of 2 mm × 2 mm was defined as one visual field, and any 10 visual fields were set as measurement targets. Elemental analysis by EPMA and structural analysis by TEM were performed at 100 times for each visual field, and δ 1- phase dross was identified among the dross in the visual field . In the crystal structure analysis by TEM, after the position of the dross to be measured was specified by EPMA in advance, the crystal structure analysis was performed by irradiating the specified position with an electron beam. Further, the longest diameter of each specified δ 1- phase dross was measured, and the number of δ 1- phase dross having a longest diameter of less than 3 to 50 μm was determined. Identified in ten fields of view, [delta] of less than longest diameter 3 ~ 50 [mu] m 1 total number of phase dross, and, based on the total area of the 10 fields of view (2 mm × 2 mm × 10), [delta] 1 phase dross The number density (pieces / cm 2 ) of Number density of delta 1- phase dross with a maximum diameter of less than 3 to 50 μm (pieces / cm) 2 ) is shown in the “Fine δ 1- phase dross number density” column in Table 1 .
[0166]
　Further, the number density (pieces / 10 m 2 ) of dross having a maximum diameter of 50 μm or more on the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheet of each test number was determined by the following method. A sample was taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet. Of the surface of the alloyed hot-dip galvanized layer of the sample, a rectangular region of 1 m × 1 m was defined as one visual field, and any 10 visual fields were set as measurement targets. In each visual field, a dross having a maximum diameter of 50 μm or more was visually observed. The total number of dross having a maximum diameter of 50 μm or more identified in 10 fields of view was counted. Based on the total number of dross having the longest diameter of 50 μm or more and the total area of ​​10 fields of view (10 m 2 ), the number density of dross having the longest diameter of 50 μm or more (pieces / 10 m 2 ) was determined. The dross, for which it is difficult to visually determine whether or not the longest diameter is 50 μm or more, was determined using a 100x optical microscope. The number density of dross having the longest diameter of 50 μm or more (pieces / 10 m 2 ) is shown in the “Coarse dross number density” column in Table 1.
[0167]
　[Dross defect evaluation test]
　The surface of the alloyed hot-dip galvanized layer of the alloyed hot-dip galvanized steel sheet of each test number was visually observed, and the above-mentioned dross having a maximum diameter of 50 μm or more was recognized as a “dross defect”.
[0168]
　The criteria for dross defect evaluation were as follows.
　　A: The number density of dross defects was 10 pieces / 10 m 2 or less
　　C: When the number density of 　dross defects exceeded 10 pieces / 10 m 2 and the
dross defect evaluation was A, it was judged that the dross defects were suppressed. On the other hand, when the dross defect evaluation is C, it is determined that the dross defect has occurred.
[0169]
　[Non-plating evaluation test]
　The presence or absence of non-plating was determined by visually observing the surface of the alloyed hot-dip galvanized layer of the alloyed hot-dip galvanized steel sheet of each test number. When non-plating was confirmed, the number density of non-plating was determined. The number density of non-plated pieces (pieces / 10 m 2 ) was determined by the following method. A sample was taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet. Of the surface of the alloyed hot-dip galvanized layer of the sample, a rectangular region of 1 m × 1 m was defined as one visual field, and any 10 visual fields were set as measurement targets. In each field of view, non-plating having a maximum diameter of 50 μm or more was visually observed. The total number of non-plated products having a maximum diameter of 50 μm or more specified in 10 fields of view was counted. Based on the total number of non-plated products having the longest diameter of 50 μm or more and the total area of ​​10 fields of view (10 m 2 ), the number density of non-plated products having the longest diameter of 50 μm or more (pieces / 10 m 2 ) was determined. For non-plating, in which it is difficult to visually determine whether or not the longest diameter is 50 μm or more, a 100-fold optical microscope was used for determination. The non-plated number density (pieces / 10 m 2 ) having the longest diameter of 50 μm or more is shown in the “non-plated number density” column in Table 1.
[0170]
　The criteria for non-plating evaluation were as follows.
　　A: There was no non-plating.
　　B: The number density of non-plated pieces was 10 pieces / 10 m 2 or less.
　　C: The number density of non-plated pieces exceeded 10 pieces / 10 m 2 .
　When the non-plating evaluations were A and B, it was judged that the non-plating was suppressed. On the other hand, when the non-plating evaluation was C, it was determined that non-plating had occurred.
[0171]
　[Surface defect evaluation test]
　The presence or absence of surface defects was determined by visually observing the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheet of each test number. Specifically, a sample was taken from the center position of an arbitrary width on the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheet. Of the surface of the alloyed hot-dip galvanized layer of the sample, a rectangular region of 1 m × 1 m was defined as one visual field, and any 10 visual fields were set as measurement targets. Surface defects were visually observed in each field of view. Specifically, in each visual field, the flaw formed by physical contact was recognized as a "surface flaw". When surface defects were confirmed, the number density of surface defects was determined. The number density of surface defects (pieces / m 2 ) was determined by the following method. The surface of the alloyed hot-dip galvanized layer of the alloyed hot-dip galvanized steel sheet of each test number was visually observed, and the total number of surface defects was counted. Surface defects can be visually confirmed by those skilled in the art. The total number of confirmed surface defects was divided by the total observed area (1 m × 1 m × 10) to obtain the number density of surface defects (pieces / m 2 ).
[0172]
　The criteria for surface defect evaluation were as follows.
　　A: There were no surface defects.
　　B: The number density of surface defects was 0.1 pieces / m 2 or less.
　　C: The number density of surface defects exceeded 0.1 / m 2 .
　When the surface defect evaluation was A, it was judged that the surface defect was suppressed. On the other hand, when the surface defect evaluation was B or C, it was determined that the surface defect had occurred.
[0173]
　[Evaluation Results] With
　reference to Table 1, in test numbers 1 to 5, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath during the hot-dip galvanizing treatment satisfy the formulas (1) to (4). It was. Therefore, in the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheet, the δ 1- phase dross having the longest diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more, and the dross having the longest diameter of 50 μm or more is generated. 10/10 m 2 or less, longest diameter 50μm or more non-plated 10/10 m 2 was less than. As a result, dross defects were suppressed, non-plating was suppressed, and surface defects were suppressed.
[0174]
　On the other hand, in test numbers 6 and 7, the free Fe concentration X and the free Al concentration Y did not satisfy the formula (1). Therefore, dross defects were confirmed on the surface of the manufactured alloyed hot-dip galvanized steel sheet. On the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheets of Test Nos. 6 and 7, there were more dross having a maximum diameter of 50 μm or more than 10 pieces / 10 m 2 . Further, in Test No. 6 and 7, [delta] of less than longest diameter 3 ~ 50 [mu] m 1 phase dross 2.5 / cm 2 was less than.
[0175]
　In test numbers 8 and 9, the free Fe concentration X and the free Al concentration Y did not satisfy the formula (2). Therefore, dross defects were confirmed on the surface of the manufactured alloyed hot-dip galvanized steel sheet. On the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheets of test numbers 8 and 9, there are more dross with a maximum diameter of 50 μm or more than 10 pieces / 10 m 2 , and the longest diameter is 3 to 50 μm. Less than δ 1- phase dross was less than 2.5 pieces / cm 2 .
[0176]
　In test numbers 10 and 11, the free Fe concentration X did not satisfy the formula (3). Therefore, non-plating was confirmed on the surface of the manufactured alloyed hot-dip galvanized steel sheet. It is probable that the metal fume was excessively generated. On the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheets of Test Nos. 10 and 11, there were more unplated pieces having a maximum diameter of 50 μm or more than 10 pieces / 10 m 2 .
[0177]
　In test numbers 12 and 13, the free Al concentration Y exceeded the upper limit of the formula (4). Therefore, surface defects were confirmed on the surface of the manufactured alloyed hot-dip galvanized steel sheet. It is probable that the top dross was generated excessively. On the surface of the alloyed hot-dip galvanized steel sheet of the alloyed hot-dip galvanized steel sheets of Test Nos. 12 and 13, the δ 1- phase dross having the longest diameter of less than 3 to 50 μm was less than 2.5 pieces / cm 2 .
Example 2
[0178]
　Similar to Example 1, a hot-dip galvanized steel sheet was manufactured using a hot-dip galvanizing facility having the same configuration as that of FIG.
[0179]
　As the steel plate, the same steel plate for automobile outer panels as in Example 1 was used. The chemical composition of the steel sheet of each test number was the same. A hot-dip galvanizing bath having a free Fe concentration X (mass%) and a free Al concentration Y (mass%) shown in Table 2 was prepared for the steel sheet. A hot-dip galvanized steel sheet was produced by performing a hot-dip galvanizing treatment using the prepared hot-dip galvanized bath. In this test, after manufacturing the hot-dip galvanized steel sheet of each test number of Example 1, the power supply of the alloying furnace was stopped (offline), and the hot-dip galvanized bath under the same bath conditions was continuously used. Manufactured plated steel sheets. The free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath were determined by the same method as in Example 1. The bath temperature in the hot-dip galvanizing bath during the hot-dip galvanizing treatment is as shown in Table 2.
[0180]
[Table 2]

[0181]
　[Evaluation test]
　[Dross number density measurement test on the surface of hot-dip galvanized layer]
　δ 1 phase with the longest diameter of less than 3 to 50 μm on the surface of the hot-dip galvanized steel sheet of the hot-dip galvanized steel sheet manufactured with each test number. Example 1 shows the number density of dross (pieces / cm 2 ), the number density of dross having a maximum diameter of 50 μm or more (pieces / 10 m 2 ), and the number density of non-plating having a maximum diameter of 50 μm or more (pieces / 10 m 2 ). It was obtained by the same method as. The number density (pieces / cm 2 ) of δ 1- phase dross having the longest diameter of less than 3 to 50 μm is shown in the “Fine δ 1- phase dross number density” column in Table 2 . The number density of dross having the longest diameter of 50 μm or more (pieces / 10 m 2 ) is shown in the “Coarse dross number density” column in Table 2. The number density of non-plated pieces having a maximum diameter of 50 μm or more (pieces / 10 m 2 ) is shown in the “Number of non-plated pieces density” column in Table 2.
[0182]
　Further, a dross defect evaluation test, a non-plating evaluation test, and a surface defect evaluation test were carried out by the same method as in Example 1. The criteria for dross defect evaluation, the criteria for non-plating evaluation, and the criteria for surface defect evaluation were all the same as in Example 1.
[0183]
　[Evaluation Results] With
　reference to Table 2, in test numbers 1 to 5, the free Fe concentration X and the free Al concentration Y in the hot-dip galvanizing bath during the hot-dip galvanizing treatment satisfy the formulas (1) to (4). It was. Therefore, in the hot-dip galvanized layer of the hot-dip galvanized steel sheet, the δ 1- phase dross having the longest diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more, and the dross having the longest diameter of 50 μm or more is 10 pieces / 10 m. The number of non-plated sheets having a maximum diameter of 50 μm or more was 10 pieces / 10 m 2 or less. As a result, dross defects were suppressed, non-plating was suppressed, and surface defects were suppressed.
[0184]
　On the other hand, in test numbers 6 and 7, the free Fe concentration X and the free Al concentration Y did not satisfy the formula (1). Therefore, dross defects were confirmed on the surface of the manufactured hot-dip galvanized steel sheet. On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheets of test numbers 6 and 7, there were more dross having a maximum diameter of 50 μm or more than 10 pieces / 10 m 2 . Further, in Test No. 6 and 7, [delta] of less than longest diameter 3 ~ 50 [mu] m 1 phase dross 2.5 / cm 2 was less than.
[0185]
　In test numbers 8 and 9, the free Fe concentration X and the free Al concentration Y did not satisfy the formula (2). Therefore, dross defects were confirmed on the surface of the manufactured hot-dip galvanized steel sheet. On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheets of test numbers 8 and 9, the number of dross having a maximum diameter of 50 μm or more is more than 10 pieces / 10 m 2 and the longest diameter is less than 3 to 50 μm δ 1. The phase dross was less than 2.5 pieces / cm 2 .
[0186]
　In test numbers 10 and 11, the free Fe concentration X did not satisfy the formula (3). Therefore, non-plating was confirmed on the surface of the manufactured hot-dip galvanized steel sheet. It is probable that the metal fume was excessively generated. On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheets of test numbers 10 and 11, there were more non-plated pieces having a maximum diameter of 50 μm or more than 10 pieces / 10 m 2 .
[0187]
　In test numbers 12 and 13, the free Al concentration Y exceeded the upper limit of the formula (4). Therefore, surface defects were confirmed on the surface of the manufactured hot-dip galvanized steel sheet. It is probable that the top dross was generated excessively. On the surface of the hot-dip galvanized layer of the hot-dip galvanized steel sheets of test numbers 12 and 13, the δ 1- phase dross having the longest diameter of less than 3 to 50 μm was less than 2.5 pieces / cm 2 .
[0188]
　Although the preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, the present invention is not limited to such examples. It is clear that a person having ordinary knowledge in the field of technology to which the present invention belongs can come up with various modifications or modifications within the scope of the technical ideas described in the claims. , These are also naturally understood to belong to the technical scope of the present invention.
Code description
[0189]
　10 Hot-dip galvanizing equipment
　101 Hot-dip galvanizing pot
　103 Hot-dip galvanizing bath
　105 Snout
　107 Sink roll
　109 Gas wiping device
　111 Alloying furnace
The scope of the claims
[Claim 1]
　It used in the method of manufacturing a galvanized steel sheet or galvannealed steel sheet, using the hot-dip galvanizing bath containing Al, a galvanizing treatment method,
　free Fe concentration in the molten zinc plating bath When defined as X (mass%) and the free Al concentration in the hot-dip galvanizing bath is defined as Y (mass%), the free Fe concentration and the free Al concentration in the hot-dip galvanizing bath are expressed by the formula (1). A
　hot-dip galvanizing treatment method comprising a concentration holding step within a range satisfying the formula (4) .
　Y ≦ 2.674X + 0.03719 (1)
　Y ≧ 0.2945X + 0.1066 (2)
　X <0.0488 (3)
　Y ≦ 0.139 (4)
[Claim 2]
　A hot-dip galvanizing treatment step of forming a hot-dip galvanizing layer on the surface of the steel plate by carrying out the hot-dip galvanizing treatment method according to claim 1 on the steel plate, and forming the
　hot-dip galvanizing layer on the surface. A method for producing an alloyed hot-dip galvanized steel sheet, which comprises an alloying process for producing an alloyed hot-dip galvanized steel sheet by performing an alloying process on the
　steel sheet.
[Claim 3]
　A method for producing a hot-dip galvanized steel sheet, comprising a hot-dip galvanizing process of forming a hot-dip galvanized layer on the surface of the steel sheet by carrying out the hot-dip galvanizing method according to claim 1
　.
[Claim 4]
　A steel plate and
　an alloyed hot-dip galvanized layer formed on the steel sheet are provided, and 2.5 　δ 1- phase dross having
　a
maximum diameter of less than 3 to 50 μm is 2.5 pieces / cm on the surface of the alloyed hot-dip galvanized layer. 2 above, and the 　dross longest diameter is more than 50μm is 10/10 m 2 or less, 　non-coating longest diameter is more than 50μm is 10/10 m 2 or less, 　galvannealed steel sheets.

[Claim 5]
　A steel plate and
　a hot-dip galvanized layer formed on the steel plate are provided, and on
　the surface of the hot-dip galvanized layer,
　a δ 1- phase dross having a maximum diameter of less than 3 to 50 μm is 2.5 pieces / cm 2 or more. A 　hot-dip galvanized steel sheet having a 　maximum diameter of 50 μm or more and
　10 pieces / 10 m 2 or less, and a
maximum diameter of 50 μm or more and 10 pieces / 10 m 2 or less