PLATED STEEL SHEET FOR HOT PRESS FORMING, HAVING EXCELLENT PLATING QUALITY, STEEL SHEET AND MANUFACTURING METHOD THEREFOR

Abstract

The steel sheet for plating according to an aspect of the present invention has a GDS profile of an Mn element and a GDS profile of an Si element, which are observed from the surface to the depth, sequentially including a maximum point and a minimum point, wherein a difference of converted concentration of Mn is 10% or more, and a difference of converted concentration of Si is 10% or more.

Claims

1-11. canceled

12. A steel sheet comprising, by weight %: 0. 1 to 4% of Mn, 0.001 to 2% of Si, 0.02 to 0.6% of C, 0.001 to 1% of Al, 0.05% or less of P, 0.02% or less of S, 1% or less of Cr, 0.01% or less of B, with a balance of Fe and inevitable impurities, wherein each of a GDS profile of an Mn element and a GDS profile of an Si element, observed from a surface thereof in a depth direction, sequentially includes a maximum point and a minimum point, a difference between a value obtained by dividing a Mn concentration at the maximum point in the GDS profile of the Mn element by a Mn concentration of a base material, and a value obtained by dividing a Mn concentration at the minimum point in the GDS profile of the Mn element by the Mn concentration of the base material (a difference of converted concentration of Mn) is 10% or more, a difference between a value obtained by dividing a Si concentration at the maximum point in the GDS profile of the Si element by a Si concentration of a base material, and a value obtained by dividing a Si concentration at the minimum point in the GDS profile of the Si element by the Si concentration of the base material (a difference of converted concentration of Si) is 10% or more, wherein when no minimum points appear within 5 um in depth, a point at a depth of 5 m is considered to be a point at which the minimum point appears.

13. The steel sheet of claim 12, wherein the steel sheet includes a base steel sheet and an Fe plating layer formed on a surface of the base steel sheet, and the surface is a surface of the Fe plating layer.

14. The steel sheet of claim 12, wherein the difference of converted concentration of Mn is 15% or more, and the difference of converted concentration of Si is 15% or more.

15. The steel sheet of claim 12, wherein a depth at which the maximum point is formed is 0.05 to 1.0 m.

16. A method for manufacturing a steel sheet for plating, comprising: preparing a base steel sheet including, by weight %: 0. 1 to 4% of Mn, 0.001 to 2% of Si, 0.02 to 0.6% of C, 0.001 to 1% of Al, 0.05% or less of P, 0.02% or less of S, 1% or less of Cr, 0.01% or less of B, with a balance of Fe and inevitable impurities, performing electroplating on the base steel sheet with an electroplating solution to form an Fe plating layer including 5 to 50 wt % of oxygen; and annealing the base steel sheet on which the Fe plating layer is formed by maintaining at a temperature range of 600 to 950 C. for 5 to 120 minutes in an annealing furnace with 1 to 70% H.sub.2-remaining N.sub.2 gas atmosphere, controlled at a dew point lower than 20 C.

17. The method for manufacturing a steel sheet for plating of claim 16 wherein an adhesion amount of the Fe plating layer is 0.5 to 3 g/m.sup.2.

18. The method for manufacturing a steel sheet for plating of claim 16, wherein the electroplating solution includes a complexing agent, and the complexing agent is at least one selected from alanine, glycine, serine, threonine, arginine, glutamine, glutamic acid and glycylglycine.

19. The method for manufacturing a steel sheet for plating of claim 16, wherein the electroplating solution includes ferrous ions and ferric ions, the ferric ions have a ratio of 5 to 60 wt % relative to total iron ions, and a total concentration of the iron ions is 1 to 80 g per 1 L of the electroplating solution.

20. The method for manufacturing a steel sheet for plating of claim 16, wherein the electroplating is performed under conditions of a solution temperature of 80 C. or lower and a current density of 3 to 120 A/dm.sup.2.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0022] FIG. 1 is a schematic diagram of a GDS profile of Mn and Si elements measured after removing a plating layer of a hot-dip plated steel sheet manufactured of a cold-rolled steel sheet electroplated with Fe.

[0023] FIG. 2 is a schematic diagram of a process in which a base steel sheet having an Fe plating layer containing oxygen formed thereon is annealed.

Best Mode for Invention

[0024] Hereinafter, a hot-dip plated steel sheet having excellent plating quality according to an aspect of the present disclosure, which was completed through the research by the present inventor, will be described in detail. It should be noted that a concentration of each element in the present disclosure means weight %, unless otherwise specified. In addition, an Fe electroplating amount is a plating amount measured as a total amount of Fe included in a plating layer per unit area, and oxygen and inevitable impurities in the plating layer were not included in the plating amount.

[0025] In addition, unless otherwise defined, a concentration and concentration profile referred to in the present disclosure mean a concentration and concentration profile measured using GDS, i.e., a glow discharge optical emission spectrometer.

[0026] Hereinafter, the present disclosure will be described in detail.

[0027] It is known that the cause of non-plating and deterioration of plating adhesion in a steel sheet containing large amounts of Mn and Si is due to surface oxides formed when alloying elements such as Mn, Si, and the like, are oxidized on the surface, during a process in which a cold-rolled steel sheet is annealed at high temperatures.

[0028] As a method of forming an oxide layer containing a large amount of oxygen to suppress the diffusion of alloying elements such as Mn, Si, and the like to the surface, an oxidation-reduction method, the method in which an oxide layer is oxidized during a temperature increase and then reduced again by maintaining the oxide layer in a reducing atmosphere, or a method in which an iron oxide is coated on a surface of a base steel sheet and heat treated, may be used. However, since the iron oxide firmly formed on the surface of the base steel sheet is a mixture of FeO, Fe.sub.3O.sub.4, and Fe.sub.2O.sub.3, which are difficult to reduce, and while the surface is reduced to metallic steel during the annealing process in a reducing atmosphere, an interface between the iron oxide layer and the base steel sheet has a slow reduction rate, making it difficult to completely reduce, and Mn and Si oxides accumulate at the interface to form a continuous oxide layer. Therefore, although wettability with molten zinc may be improved, the oxide layer may easily crumble, causing a problem in which the plating layer is peeled off.

[0029] Meanwhile, when an internal oxidation method at annealing in which alloying elements such as Mn, Si, and the like, are oxidized inside steel, by increasing oxygen partial pressure or a dew point inside an annealing furnace during a heat treatment process, is applied, Mn and Si oxides are preferentially formed on a surface of the steel during the heat treatment process, and then Mn and Si are oxidized by oxygen diffused into the steel, thereby inhibiting surface diffusion. Accordingly, a thin oxide film is formed on the surface of the base steel sheet, and if a surface of a cold-rolled steel sheet is not completely homogeneous before annealing, or if there is a local deviation in oxygen partial pressure, temperature, or the like, the wettability is uneven during hot-dip galvanizing, causing non-plating, or if the thickness of the oxide film is uneven during an alloying heat treatment process after galvanizing, causing a difference in a degree of alloying, there is a tendency for linear defects that can be easily identified with the naked eye to occur.

[0030] In order to solve the problems of the above technology, the present inventors have attempted to manufacture a hot-dip plated steel sheet having an attractive surface and no plating peeling problem by controlling the presence of Mn and Si, which are oxidizing elements, on the surface of the steel sheet for plating as follows.

[0031] That is, the steel sheet according to an embodiment of the present disclosure may have the following characteristics in terms of the GDS concentration profile of Mn and Si. A steel sheet for plating of the present disclosure will be described in detail with reference to the GDS profile of FIG. 1.

[0032] FIG. 1 is a graph schematically illustrating a typical GDS profile of an alloy element that may appear from a surface portion after a galvanized layer is removed from a hot-dip plated steel sheet including the steel sheet of the present disclosure. In the graph, a vertical axis represents a concentration of alloying elements such as Mn, Si, and the like, and a horizontal axis represents a depth.

[0033] As can be seen from a typical example of the GDS profile of the Mn element of the present disclosure illustrated in FIG. 1, the steel sheet of the present disclosure may have a very low concentration of Mn on the surface, and may have a concentration gradient in the form of maximum and minimum points appearing sequentially from the surface in a depth direction. Here, sequentially having the maximum and minimum points does not necessarily mean that the maximum point appears first in the depth direction from the surface (interface), and in some cases, means that the minimum point may appear first, but the maximum point and the minimum point should appear sequentially thereafter. However, in some embodiments, the minimum point may not appear, and in this case, the internal concentration in the 5 m depth region may be a concentration of the minimum point. In addition, the concentration of alloying elements on the surface may have a lower value than the concentration at the maximum point, but in some cases, a minimum point with a low concentration of alloying elements may appear between the surface and the maximum point.

[0034] In the GDS concentration profile exemplified in FIG. 1 above, although not limited thereto, the surface layer portion corresponds to an plating layer with a low concentration of alloying elements since the alloying elements are not greatly diffused from a base steel sheet, the maximum point corresponds to a region in which internal oxides of the alloying elements formed near an interface between the Fe plating layer and base steel sheet are concentrated, and the minimum point appearing on a side of the base steel sheet in the Fe plating layer corresponds to a region in which alloying elements diffuse to the Fe plating layer not including the alloying elements and are diluted, or a region in which alloying elements diffuse to the maximum point at which internal oxidation occurs and are depleted.

[0035] In an embodiment of the present disclosure, the maximum point may be formed at a depth of 0.05 to 1.0 m from a surface of the steel sheet. If the maximum point appears in a region deeper than the region described above, it may not be determined to be a maximum point due to the effect of the present disclosure. In addition, the minimum point can be formed at a location within 5 m of depth of the surface of the steel sheet. As described above, if the minimum point is not formed at the point within 5 m of depth, the 5 m of depth may be determined to be a point at which the minimum point is formed. Since the concentration at the depth of 5 m is substantially the same as the concentration of a base material, it can be considered to be a point at which the concentration no longer decreases.

[0036] In this case, as the difference between the converted concentration at the maximum point of the corresponding element (a value obtained by dividing the concentration thereof at the corresponding point by the concentration of the base material, expressed in units of %) and the converted concentration at the minimum point thereof in the Mn concentration profile and the Si concentration profile increases, Mn and Si diffusing to the surface may be reduced, which is important. In an embodiment of the present disclosure, the converted concentration value at the maximum point of Mn and Sithe converted concentration value at the minimum point Mn and Si may respectively be 10% or more.

[0037] As a result of experiments conducted by the present inventors under various conditions, when the above-described conditions are satisfied, a hot-dip plated steel sheet having good plating adhesion and in which non-plating does not occur during hot-dip plating, may be obtained. However, if the difference between the converted concentrations at the maximum point and the minimum point of Mn and Si is less than 10%, there may be a problem in which point or linear non-plating occurs or plating peeling occurs. That is, by controlling the difference of converted concentration to a certain level or higher, it is possible to prevent the formation of oxides of Mn and Si on the surface, so that a hot-dip plated steel sheet having an attractive surface and good plating adhesion may be manufactured, and even if a subsequent alloying heat treatment process is performed, it is possible to suppress the occurrence of defects such as linear defects on the surface. The greater the difference between the converted concentration values, the more advantageous it is, so there is no need to set an upper limit for the values. However, considering the contents of the elements included, the difference of converted concentration values may be set to 200% or less for both Mn and Si. In another embodiment of the present disclosure, the difference of converted concentration of Mn and Si may be 15% or more or 20% or more.

[0038] Hereinafter, the GDS analysis method performed in the present disclosure is described in detail.

[0039] For the GDS concentration analysis, a hot-dip plated steel sheet is cut to a size of 30 to 50 mm in length, washed first in a NaOH solution at room temperature, and then dipped in a 20 to 40 vol % hydrochloric acid solution to remove a plating layer.

[0040] To prevent damage to a surface of a base steel sheet during a dissolution process of a plating layer, an acid solution was removed within 10 seconds when bubble generation due to a reaction between the plating layer and the acid solution is stopped, and the base steel sheet was washed using pure water and dried. If it is a steel sheet for plating that has not yet been hot-dip plated, it may be analyzed without removing the plating layer.

[0041] The GDS concentration profile measures concentrations of all elements contained in the steel sheet at intervals of 1 to 5 nm in a thickness direction of the steel sheet. Irregular noise may be included in the measured GDS profile, an average concentration profile was obtained by applying a Gaussian filter with a cutoff value of 100 nm to the measured concentration profile to obtain the maximum and minimum points of the Mn and Si concentrations, and the concentration values and depths at the maximum and minimum points of the concentrations were respectively obtained from the noise-removed profile. In addition, it should be noted that the maximum and minimum points mentioned in the present disclosure were calculated as maximum and minimum points only when the difference between the maximum point and the minimum point in the depth direction was 10 nm or more.

[0042] The steel sheet for plating targeted in the present disclosure may include a base steel sheet and an Fe plating layer formed on the base steel sheet. The composition of the base steel sheet is not particularly limited.

[0043] However, if the steel sheet is a steel sheet having a composition which easily forms oxides on the surface, containing 0.1 to 4 wt % of Mn and 0.001 to 2 wt % of Si, plating properties may be advantageously improved by the present disclosure. An upper limit of a concentration of Mn of the base steel sheet is not particularly limited, but considering the composition commonly used, the upper limit may be limited to 4 wt %. In addition, although a lower limit of the concentration of Mn is not particularly limited, if a composition contains less than 0.1 wt % of Mn, the surface quality of a hot-dip plated steel sheet is attractive, even if a Fe plating layer is not formed, so there is no need to perform Fe electroplating thereon. An upper limit of a Si concentration is not particularly limited, but considering the composition commonly used, the upper limit may be limited to 2.0 wt % or less, and if the Si concentration is less than 0.001 wt %, the quality of the hot-dip plating is good, even if the method of the present disclosure is not performed, so there is no need to perform the method of the present disclosure.

[0044] Since Mn and Si are elements affecting the plating property, the concentrations of Mn and Si may be limited as described above, but in the present disclosure, the remaining elements of the base steel sheet are not particularly limited.

[0045] However, considering the fact that non-plating and deterioration of plating adhesion may occur severely in the steel sheet containing a large amount of alloying elements, in an embodiment of the present disclosure, the base steel sheet may include, by weight %: 0.1 to 4% of Mn, 0.001 to 2% of S, 0.02 to 0.6% of C, 0.001 to 1% of Al, 0.05% or less of P, 0.02% or less of S, 1% or less of Cr, 0.01% or less of B, with a balance of Fe and inevitable impurities. P, S are impurities, which are advantageous when not added, and Cr and B are optional elements and do not need to be added, so lower limits thereof are not set. In addition to the elements described above, the base steel sheet may further include elements such as Ti, Mo, and Nb in a total amount of 1.2% or less. The base steel sheet is not particularly limited, but in an embodiment of the present disclosure, a cold-rolled steel sheet or a hot-rolled steel sheet may be used as the base steel sheet.

[0046] In an aspect of the present disclosure, a hot-dip plated steel sheet including the steel sheet for plating may be provided, and the hot-dip plated steel sheet may include a steel sheet for plating and a hot-dip plated layer formed on a surface of the steel sheet for plating. In this case, any commercially available hot-dip plated steel sheet can be used, and there are no specific restrictions on the type thereof.

[0047] Next, an exemplary embodiment of a method for manufacturing a steel sheet for plating and a hot-dip plated steel sheet having the advantageous effects described above is described. According to an embodiment of the present disclosure, the steel sheet for plating may be manufactured by a process including: preparing a base steel sheet; performing electroplating on the base steel sheet to form an Fe plating layer including 5 to 50 wt % of oxygen; and annealing the base steel sheet on which the Fe plating layer is formed.

[0048] After electroplating with Fe containing 6.2 wt % of oxygen is performed on a cold-rolled steel sheet for hot press forming including 1.3% of Mn, 0.3% of Si, and other alloying elements to have an iron adhesion amount of 1.95 g/m.sup.2, the electroplated cold-rolled steel sheet was annealed in an atmosphere of N.sub.2-5% H.sub.2, a dew point of 40 C., and a temperature of 800 C. for 53 seconds, and then cooled. The atmosphere was maintained the same throughout the entire annealing process, and when a sample was collected from the cooled steel sheet and then a cross-section thereof was observed using a transmission electron microscope, it could be confirmed that particle-type Mn and Si oxides were formed at an interface between the iron electroplating layer and the base steel sheet, whereas almost no Mn and Si oxides were formed on a surface of the electroplating layer. In particular, when this state is analyzed using a GDS profile, as shown in FIG. 1, maximum values of the Mn and Si concentrations appear immediately below the surface of the steel sheet (including an Fe plating layer), and minimum values of the Mn and Si concentrations may appear at a deeper location thereof. In some cases, the minimum value may not clearly appear and a trend in which the concentration gradually decreases may appear, but the maximum value may be clearly observed.

[0049] This phenomenon is because an Fe plating layer with a high oxygen content was formed before annealing. That is, when the iron electroplating layer contains 5 to 50 wt % of oxygen, and when annealed in an annealing furnace in a reducing atmosphere, oxygen in the iron electroplating layer oxidizes alloying elements such as Mn, Si, and the like, diffusing from the base steel sheet to the surface and is accumulated at the interface between the iron electroplating layer and the base steel sheet. Therefore, as illustrated in the graph of FIG. 1, when the concentration is measured with GDS, a maximum point with high concentrations of Mn, Si, and the like, is confirmed at a depth corresponding to the thickness of the iron electroplating layer from the surface. Meanwhile, an alloying element having a slow diffusion rate, such as Mn, or the like, cannot diffuse quickly from the base steel sheet even when the concentration thereof is diluted by the iron electroplating layer or the dissolved Mn is depleted due to internal oxidation, so a minimum point may exist after the maximum point obtained by the measured GDS concentration. However, since Si rapidly diffuses from the inside during the annealing process, and internal oxidation is continuously performed at the interface between the iron electroplating layer and the base steel sheet, oxides are accumulated, a minimum point may not be confirmed in the GDS concentration analysis. Therefore, the fact that the minimum point does not appear in the GDS concentration profile means that the alloying elements such as Mn, Si, and the like, were oxidized by the iron electroplating layer and effectively suppressed from the diffusion to the surface.

[0050] Unlike an oxide formed at high temperatures, when an iron electroplating layer containing a large amount of oxygen is formed and annealed, reduction occurs simultaneously not only on the surface of the iron electroplating layer but also at the interface between the iron electroplating layer and the base steel sheet. In this case, the reduced iron is bonded by mutual diffusion with the base steel sheet, and Mn and Si react with oxygen in the Fe plating layer to form oxides in the form of particles or discontinuous plates at the interface between the iron electroplating layer and the base steel sheet, so that good adhesion between the iron electroplating layer and the base steel sheet may be maintained. In addition, the uniformly formed iron electroplating layer may suppress the formation of surface oxides and reduce the concentration of alloying elements such as Mn, Si, and the like, dissolved on the surface of the steel sheet, thereby promoting an alloying reaction with the galvanized layer, thereby obtaining a uniformly hot-dip alloy-plated steel sheet without surface defects.

[0051] Unlike the oxidation reduction method, in the internal oxidation method at annealing, since a layered oxide layer is not formed, excellent properties in improving the plating adhesion during hot-dip plating a steel sheet for hot press forming containing a large amount of alloying elements such as Mn, Si, and the like, are illustrated, but since water vapor inside the annealing furnace inevitably oxidizes the surface of the steel sheet first, and then oxygen penetrates thereinto, it is impossible to fundamentally remove the surface oxide. As a result, if the surface of the cold-rolled steel sheet is not completely homogeneous before annealing, or if a local deviation such as oxygen partial pressure, temperature, and the like, during with a hot-dip plating annealing occurs, wettability solution is uneven, resulting in non-plating, or if a thickness of an oxide film is uneven during an alloying heat treatment process after plating, in the case of galvanizing, resulting in a difference in a degree of alloying, which can cause a problem such as linear defects which can be easily identified with the naked eye.

[0052] To manufacture an attractive hot-dip plated steel sheet without plating peeling problems, by suppressing the surface diffusion of alloying elements by Fe plating containing a large amount of oxygen, it is recommended that an iron electroplating layer containing 5 to 50 wt % of oxygen is formed on the base steel sheet to have an iron adhesion amount of 0.5 to 3.0 g/m.sup.2, the temperature is increased to 600 to 950 C. so that the mechanical properties of the steel sheet may be secured, and then cooled to perform hot-dip plating.

[0053] In an embodiment of the present disclosure, the Fe plating layer may be formed through a continuous plating process, and the Fe plating amount herein may be 0.5 to 3.0 g/m.sup.2 based on the Fe adhesion amount. If the Fe plating amount is less than 0.5 g/m.sup.2, a diffusion suppression effect of alloying elements by the Fe plating layer may be insufficient in a common continuous annealing process. In addition, even if the Fe plating amount exceeds 3.0 g/m.sup.2, the diffusion suppression effect of alloying elements may be further increased, but to secure a high plating amount, a plurality of plating cells should be operated, and when an insoluble anode is used, the electroplating solution becomes rapidly acidic, which reduces the plating efficiency and causes sludge to be generated, which may be uneconomical. In another embodiment of the present disclosure, the Fe plating amount may be 1.0 to 2.0 g/m.sup.2. When an Fe plating layer is formed and then internal oxidation is performed, internal oxides are formed at an interface between the Fe plating layer and the base steel sheet or directly below the interface, so the maximum points of the concentrations of Mn and Si exist in a region in the range of 0.05 to 1.0 m. The Fe plating amount of 0.5 to 3.0 g/m.sup.2 of the present disclosure may correspond to a thickness of 0.05 to 0.4 m after annealing.

[0054] In addition, the Fe plating layer having the above-described high oxygen concentration may have maximum and minimum points in the GDS concentration profile of Mn and Si elements formed inside the steel sheet for plating by controlling the temperature, dew point temperature, and atmosphere in a subsequent annealing process, and is configured so that the converted concentration at the maximum point and the converted concentration at the minimum point may satisfy a numerical range limited in an embodiment of the present disclosure. In consideration thereof, in an embodiment of the present disclosure, the concentration of oxygen in the Fe plating layer may be 5 to 50 wt %, and in another embodiment, the concentration of oxygen in the Fe plating layer may be 10 to 40 wt %. In order to obtain the surface oxide suppression effect, the amount of oxygen in the Fe plating layer should be sufficient. Even if the concentration of oxygen in the Fe plating layer is less than 5 wt %, the surface oxide suppression effect may be obtained by increasing the Fe plating amount, but in order to obtain such an effect, plating should be performed in excess of 3.0 g/m.sup.2, which may cause various problems as described above. In addition, since it is difficult to sequentially form the maximum points and minimum points in the GDS profile of Mn and Si when the content of oxygen is less than 5 wt %, in an embodiment of the present disclosure, the content of oxygen in the Fe plating layer is controlled to be 5 wt % or more. Meanwhile, the surface oxide suppression effect during annealing can be further increased as the concentration of oxygen in the Fe plating layer increases, but since it is difficult to obtain a plating layer in excess of 50 wt % using a common electroplating method, an upper limit thereof may be limited to 50 wt %. In another embodiment of the present disclosure, the concentration of oxygen in the Fe plating layer may be limited to 10 to 40%.

[0055] In an embodiment of the present disclosure, an annealing temperature may be 600 C. to 950 C. based on a temperature of the steel sheet in a soaking section. If the annealing temperature is too low, since a structure of the cold-rolled steel sheet is not properly be recovered or not recrystallized, so it is difficult to secure mechanical properties such as strength, elongation, and the like, of the steel sheet, and if the annealing temperature is higher than 950 C., alloying elements in the steel rapidly diffuse to the surface, resulting in poor quality of hot-dip plating, and the operation is performed unnecessarily at high temperatures, which may be uneconomical.

[0056] Meanwhile, in an embodiment of the present disclosure, a dew point temperature inside the annealing furnace is not necessarily limited thereto, but may be lower than 20 C. When the dew point temperature is maintained below 20 C., since a separate humidifying device is not required to increase the dew point, which may be economical. In addition, in the present disclosure, since an Fe plating layer having a high oxygen concentration is formed, even if internal oxidation by the atmosphere is not necessarily induced, it is possible to sufficiently prevent alloying elements such as Mn, Si, and the like from diffusing to the surface. A lower limit of the dew point temperature is not specifically set. However, maintaining the dew point below 90 C. may not be industrially advantageous, such as using very high-purity gas, so the lower limit of the dew point may be set to-90 C. in consideration thereof. According to another embodiment of the present disclosure, when the temperature of the steel sheet is 600 to 950 C., the dew point herein may be 70 to 30 C.

[0057] In addition, in order to prevent oxidation of the base steel sheet and the Fe plating layer during annealing, a concentration of hydrogen in the atmosphere gas during annealing may be set to 1% or more by volume %. When the hydrogen concentration is less than 1%, a trace amount of oxygen inevitably included in H.sub.2 and N.sub.2 gases cannot be effectively oxidized and removed, which increases the oxygen partial pressure and can cause surface oxidation of the base steel sheet. Meanwhile, if the hydrogen concentration exceeds 70%, there may be a risk of explosion in the event of gas leakage and the cost of high-hydrogen work increases, so the hydrogen concentration may be set to 70% or less. Except for the impurity gases which are inevitably included other than the hydrogen (H.sub.2), it may be substantially nitrogen (N.sub.2).

[0058] According to an embodiment of the present disclosure, a holding time after reaching a target temperature during annealing may be limited to 5 to 120 seconds. In order to sufficiently transfer heat to the inside of the base steel sheet during annealing and to obtain uniform mechanical properties in the thickness direction, the holding time is required to be maintained at the target temperature during annealing for 5 seconds or longer. Meanwhile, if the holding time during annealing at high temperatures becomes excessively long, the diffusion of alloying interfering elements through the Fe plating layer increases, which increases the amount of surface oxides generated, and as a result, the quality of hot-dip plating deteriorates, so the holding time may be limited to 120 seconds or less.

[0059] Hereinafter, based on the above-described contents, an effect of suppressing surface diffusion of Mn and Si during annealing in a high dew temperature atmosphere of a cold-rolled steel sheet having an Fe plating layer containing a large amount of oxygen will be described in more detail with reference to FIG. 2.

[0060] FIG. 2 schematically illustrates a phenomenon which occurs inside a steel sheet as a temperature of the steel sheet increases according to the conditions of the present disclosure.

[0061] FIG. 2 (a) illustrates a schematic cross-sectional diagram of a base steel sheet on which an Fe plating layer containing a large amount of oxygen is formed. The base steel sheet includes alloying elements such as Mn, Si, and the like, and the Fe plating layer includes 5 to 50 wt % of oxygen and impurities which are inevitably incorporated during plating, and the remainder is comprised of Fe.

[0062] FIG. 2 (b) illustrates a state in which a cold-rolled steel sheet, electroplated with Fe, is heated to about 300 to 500 C. in a nitrogen atmosphere containing 1 to 70% H.sub.2. A surface of the Fe plating layer containing a large amount of oxygen is gradually reduced and the oxygen is removed, and internal oxides of elements such as Mn, Si, and the like, diffused from the base steel sheet begin to be generated at an interface between the Fe plating layer and the base steel sheet, and as the temperature increases the oxides at grain boundaries grow coarsely.

[0063] FIG. 2 (c) illustrates a schematic cross-sectional view of a base steel sheet when the temperature is increased from 500 to 700 C. in the same reducing atmosphere. The Fe plating layer is almost completely reduced, thereby forming ferrite with lower Mn and Si concentrations compared to that of the base steel sheet, and as oxygen in the Fe plating layer is gradually depleted, Mn and Si begin to penetrate the Fe plating layer and slowly diffuse to the surface of the Fe plating layer.

[0064] FIG. 2 (d) illustrates a cross-sectional schematic diagram of a steel sheet that has been annealed at a temperature within a range of 600 to 950 C. Except for internal oxides of elements such as Mn, Si, and the like, in the iron electroplating layer, oxygen dissolved in metallic steel is completely removed, and the generated internal oxides generated are generally spherical or short plate-shaped. In addition, due to grain growth, the iron electroplating layer may form single grains with the base steel sheet. However, the form of the internal oxides is not necessarily generated in the form of particles, and depending on elongation of the cold-rolled steel sheet, the composition of steel, the atmosphere in the annealing furnace, and the content of oxygen contained in the iron electroplating layer, the grains of the base steel sheet and the iron electroplating layer may appear to be distinct, or short linear oxides may be formed along the interface between the iron electroplating layer and the base steel sheet or grain boundaries within the base steel sheet.

[0065] After the annealing operation, the annealed steel sheet may be cooled. Since the cooling conditions in the cooling operation after the annealing operation do not significantly affect the surface quality of a final product, that is, the plating quality, there is no need to specifically limit the cooling conditions in the present disclosure. However, in order to prevent oxidation of iron elements during the cooling process, an atmosphere which is at least reducing for iron may be applied.

[0066] According to an embodiment of the present disclosure, a hot-dip plated layer may be formed by hot-dip plating the steel sheet for plating obtained by the above-described process. The hot-dip plating method in the present disclosure is not particularly limited. The type of plating of the present disclosure is not particularly limited as long as it is a plating method used for a steel sheet for hot press forming, and some non-limiting examples thereof may include hot-dip galvanizing, hot-dip aluminum plating, or the like. It should be noted that it is not necessary to use pure zinc or aluminum in hot-dip galvanizing or hot-dip aluminum plating and alloy plating including magnesium, aluminum, zine, or alloying elements included in other plating layers may also be sufficiently used.

[0067] In addition, in the present disclosure, since any base steel sheet having the alloy composition described above may be applied without limitation as the base steel sheet of the steel sheet for plating or hot-dip plated steel sheet according to the present disclosure, the method of manufacturing the base steel sheet may not be specifically limited.

[0068] In an embodiment of the present disclosure, an Fe plating layer can be formed on a surface of a base steel through an electroplating and method, an oxygen concentration of the formed Fe plating layer may be controlled by appropriately controlling the conditions of the electroplating solution and the plating conditions.

[0069] That is, in the present disclosure, in order to form an Fe plating layer, an electroplating solution may be used, the electroplating solution including: iron ions including ferrous ions and ferric ions; a complexing agent; and inevitable impurities, wherein a concentration of the ferric ions of the iron ions is 5 to 60% by weight.

[0070] According to an embodiment of the present disclosure, the electroplating solution includes ferrous ions and ferric ions. In order to obtain high plating efficiency, it may be advantageous that the electroplating solution includes only ferrous ions. However, when only ferrous ions are included, the electroplating solution deteriorates and the plating efficiency rapidly decreases, which may cause a deviation in quality thereof in a continuous electroplating process, the electroplating solution may further include the ferric ions. In this case, the concentration of the ferric ions is preferably 5 to 60 wt %, and is more preferably 5 to 40 wt % of the total sum of ferrous and ferric ions. When the concentration is less than 5%, a rate at which ferric iron is reduced to ferrous iron at a cathode is less than a rate at which ferrous iron is oxidized to ferric iron at an anode, so the concentration of ferric iron rises rapidly, and pH drops rapidly and plating efficiency continues to deteriorate. On the other hand, when the concentration of ferric ions exceeds 60%, a reaction amount in which ferric iron is reduced to ferrous iron at the cathode is greatly increased, compared to a reaction amount in which ferrous iron is reduced and precipitated as metallic steel, so the plating efficiency decreases significantly and the plating quality deteriorates. Therefore, considering the equipment and process characteristics such as a plating amount, working current density, a solution supply amount, an amount of solution lost by being deposited on a strip, a rate of a change in concentration due to evaporation, and the like, it is preferable that the concentration of ferric ions among the iron ions is 5 to 60 wt %.

[0071] The concentration of iron ions is preferably 1 to 80 g per 1 L of the electroplating solution, and is more preferably 10 to 50 g per 1 L. When the concentration of iron ions is less than 1 g/L, there is a problem that the plating efficiency and plating quality deteriorate rapidly. On the other hand, when the concentration of iron ions exceeds 80 g/L, solubility may be exceeded and precipitation may occur, and loss of a raw material due to loss of the solution in the continuous plating process increases, which may be uneconomical.

[0072] The electroplating solution of the present disclosure includes a complexing agent, and in order to maintain high plating efficiency without generating sludge while containing a large amount of ferric iron, it is preferable to use an amino acid or an amino acid polymer as a complexing agent.

[0073] An amino acid refers to an organic molecule in which a carboxyl group (COOH) and an amine group (NH.sub.2) are combined, and an amino acid polymer refers to an organic molecule formed by polymerizing two or more amino acids, and an amino acid polymer has properties of complexing agents, similar to that of an amino acid. Therefore, in the following description, an amino acid and an amino acid polymer are collectively referred to as an amino acid.

[0074] When an amino acid is dissolved in neutral water, since amine combines with hydrogen ions to acquire a positive charge, and a carboxyl group dissociates the hydrogen ion to acquire a negative charge, the amino acid molecule maintains a neutral charge. Meanwhile, when the solution becomes acidic, since the carboxyl group recombines with the hydrogen ions, making the charge neutral, and amine has a positive charge, the amino acid molecule forms a cation. In other words, an amino acid forms a neutral charge or cation in a slightly acidic aqueous solution.

[0075] When an amino acid is added to an acidic electrolyte containing iron ions, the amino acid is complexed with ferrous and ferric ions, and the iron ions complexed with the amino acid maintain a cationic state even in the complexed state. Therefore, it exhibits electrically opposite properties to the common complexing agent having a plurality of carboxyl groups, having a negative charge in a weakly acidic aqueous solution.

[0076] In addition, compared to the complexing agent including a plurality of carboxyl groups such as citric acid, EDTA, and the like, an amino acid forms fewer bonds with iron ions and has a weaker bonding force, but the bonding force with ferric ions which generates sludge is sufficiently strong, so precipitation due to ferric ions may be prevented. In addition, since the ferric ions may maintain cations even when the ferric ions are complexed, the ferric ions can be easily transferred to a cathode and reduced to ferrous ions to participate in a plating reaction, while the movement thereof to an anode is suppressed, so a production rate of the ferric ions is slowed down, so that the concentration of ferric ions is maintained at a constant level even when continuous plating is performed for a long period time, the plating efficiency is maintained constant, and there is no need to replace an electrolyte.

[0077] Meanwhile, in a continuous electroplating process, when the iron ions in a solution are exhausted by plating, the solution becomes acidic, and even when the same amount of iron ions is precipitated, a change in pH in a solution containing both ferric ions and ferrous ions is reduced compared to a solution containing only ferrous ions. When pH increases, some ferric ions combine with hydroxide ions, and when pH decreases, hydroxide ions are separated and neutralized, so the solution containing the ferric ions acts as a pH buffer by slowing down the change in pH without a separate pH buffer, so that the electroplating efficiency may be maintained at a constant level in a continuous electroplating process.

[0078] Therefore, by using an amino acid as a complexing agent, sludge may be prevented, and not only ferrous ions but also ferric ions may be used as a plating material, and when ferrous ions and ferric ions are mixed and used, the change in pH of the solution may be slowed down, and the accumulation of ferric ions may be easily prevented, so that the electroplating efficiency and plating quality may be maintained to be constant in a continuous electroplating process.

[0079] Meanwhile, the complexing agent is preferably added in an amount so that a molar concentration ratio between the iron ion and the complexing agent is 1:0.05 to 2.0, and more preferably 1:0.5 to 1.0. When the molar concentration ratio is less than 0.05, the ferric ions excessively contained, cannot be suppressed from combining with hydroxide ions or oxygen to form sludge, and even when ferric ions are not included, the plating efficiency is greatly reduced, and furthermore, burning is induced, resulting in poor plating quality. On the other hand, even when the molar concentration ratio exceeds 2.0, the sludge suppression effect and plating quality are maintained, but the plating efficiency decreases due to an increased overvoltage, and since an excessive amount of amino acid is unnecessarily included, which is relatively expensive compared to a raw material containing iron ions such as iron sulfate, or the like, the cost of raw materials increases, which may be uneconomical.

[0080] The complexing agent is preferably at least one selected from amino acids or amino acid polymers. For example, the complexing agent may be at least one selected from alanine, glycine, serine, threonine, arginine, glutamine, glutamic acid, and glycylglycine.

[0081] When the amino acid is used as a complexing agent, and electroplating is performed at a current density of 3 to 120 A/dm.sup.2 while maintaining a temperature of a solution at 80 C. or lower and pH at 2.0 to 5.0, an Fe plating layer having high plating efficiency and high oxygen concentration may be obtained.

[0082] The temperature of the Fe electroplating solution does not significantly affect the quality of the Fe plating layer, but when the temperature of the Fe electroplating layer exceeds 80 C., evaporation of the solution becomes severe and the concentration of the solution continuously changes, making uniform electroplating difficult.

[0083] If the pH of the Fe electroplating solution is less than 2.0, the electroplating efficiency decreases, which is not suitable for a continuous plating process. If the pH of the Fe electroplating solution exceeds 5.0, the plating efficiency increases, but sludge in which iron hydroxide precipitates is generated during continuous electroplating, causing problems such as pipe clogging and contamination of rolls and equipment.

[0084] If the current density is less than 3 A/dm.sup.2, a plating overvoltage of the cathode decreases and the Fe electroplating efficiency decreases, so it is not suitable for a continuous plating process. If the current density exceeds 120 A/dm.sup.2, burning occurs on the plating surface, causing the electroplating layer to become uneven and the Fe plating layer to easily fall off.

[0085] As described above, in the present disclosure, 5 to 50 wt % of oxygen is preferably contained in the Fe plating layer. The causes in which oxygen is incorporated into the Fe plating layer are as follows. In the process in which iron is precipitated on the surface of the steel sheet to which a cathode is applied, and at the same time, as hydrogen ions are reduced to hydrogen gas, the pH increases. Therefore, both ferrous and ferric ions are temporarily combined with OH.sup. ions and can be incorporated together when the Fe plating layer is formed. If an anionic complexing agent such as acetic acid, lactic acid, citric acid, or EDTA is used, the iron ions combined with OH.sup. ions in the complexing agent have an average negative charge, and when a cathode is applied for electroplating, repulsion electrically occurs, which suppresses the incorporation into the Fe plating layer. On the other hand, amino acids are electrically neutral at pH 2.0 to 5.0, and have cations in strong acids below pH 2.0. Even if 1 to 2 OH.sup.s are combined to the iron ion combined with the amino acid, the amino acids have cations, so electrical attraction with the cathode performing electroplating occurs, causing a large amount of oxygen to be incorporated therein. Therefore, if an amino acid is used as a complexing agent so that a molar concentration ratio between iron ions and amino acids is 1:0.05 to 1:2.0, and Fe electroplating is performed while maintaining pH at 2.0 to 5.0, an Fe plating layer containing 5 to 50 wt % oxygen can be obtained while having high plating efficiency and suppressing sludge generation.

[0086] In order to secure the quality of hot-dip plating of the steel sheet containing Mn and Si, it is preferable that a plating amount of the Fe plating layer is 0.5 to 3.0 g/m.sup.2 based on the iron concentration. An upper limit of the Fe plating amount is not particularly limited, but if the Fe plating amount exceeds 3.0 g/m.sup.2 in a continuous plating process, a plurality of plating cells are required or a production rate thereof is reduced, which may be uneconomical. In addition, if an Fe electroplating amount is large, the Fe electroplating solution is rapidly transformed in a continuous process, causing the pH to drop and the plating efficiency to decrease significantly, making the management of solution difficult. On the other hand, if the Fe electroplating amount is less than 0.5 g/m.sup.2, since oxygen contained in the Fe plating layer is quickly reduced and removed, Mn and Si diffuse from the base steel sheet so that the formation of surface oxides may not be effectively suppressed, so that there is a problem in that the quality of hot-dip plating deteriorates. The Fe plating amount is an iron concentration contained in the plating layer, and when the Fe plating layer is completely reduced during annealing, it has a thickness of about 0.05 to 0.4 m.