JP2014040652A - High-strength steel plate and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-strength steel plate excellent in chemical conversion, and corrosion resistance after electrodeposition coating even when having a large content of Si or Mn, and a manufacturing method thereof.SOLUTION: When a steel plate containing C of 0.03-0.35%, Si of 0.01-0.50%, Mn of 3.6-8.0%, Al of 0.01-1.0%, P≤0.10%, S≤0.010% by mass% and the remainder consisting of Fe and inevitable impurities is continuously annealed, the maximum arrival temperature of the steel plate in an annealing furnace is 600°C or more and 750°C or less, a steel plate passing time at the steel plate temperature of 600°C or more and 750°C or less is 30 seconds or more and 10 minutes or less, and a dew point in the atmosphere is -10°C or less.

Description

  The present invention relates to a high-strength steel sheet having excellent chemical conversion property and corrosion resistance after electrodeposition coating, and a method for producing the same, even when the content of Si or Mn is large.

In recent years, from the viewpoint of improving the fuel efficiency of automobiles and improving the collision safety of automobiles, there is an increasing demand for reducing the thickness of the vehicle body by increasing the strength of the vehicle body material and reducing the weight of the vehicle body. Therefore, application of high-strength steel sheets to automobiles is being promoted.
In general, steel plates for automobiles are used after being coated, and as a pretreatment for the coating, a chemical conversion treatment called a phosphate treatment is performed. The chemical conversion treatment of the steel sheet is one of the important treatments for ensuring the corrosion resistance after painting.

In order to increase the strength and ductility of the steel sheet, addition of Si and Mn is effective. However, during continuous annealing, Si and Mn are oxidized even when annealing is performed in a reducing N ₂ + H ₂ gas atmosphere where Fe oxidation does not occur (reducing Fe oxide), and are selected as the outermost layer of the steel sheet. In particular, a surface oxide (SiO ₂ , MnO, etc., hereinafter referred to as a selective surface oxide) containing Si and Mn is formed. Since this selective surface oxide inhibits the formation reaction of the chemical conversion film during the chemical conversion treatment, a fine region (hereinafter also referred to as “ske”) where the chemical conversion film is not formed is formed, and the chemical conversion treatment performance is lowered.

As a conventional technique for improving chemical conversion properties of a steel sheet containing Si or Mn, Patent Document 1 discloses a method of forming an iron coating layer of ^{20 to} 1500 mg / m ² on a steel sheet using an electroplating method. Yes. However, in this method, there is a problem that the cost is increased due to the additional steps required for the electroplating equipment.

  Moreover, in patent document 2, Mn / Si ratio is prescribed | regulated, and patent document 3 is improving the phosphate processability by adding Ni, respectively. However, the effect depends on the contents of Si and Mn in the steel sheet, and it is considered that further improvement is necessary for the steel sheet having a high content of Si and Mn.

Furthermore, in Patent Document 4, an internal oxide layer made of an oxide containing Si is formed within a depth of 1 μm from the surface of the steel sheet base by setting the dew point during annealing to −25 to 0 ° C., and the steel sheet surface length A method is disclosed in which the proportion of the Si-containing oxide in 10 μm is 80% or less. However, in the case of the method described in Patent Document 4, since the area for controlling the dew point is premised on the entire inside of the furnace, the controllability of the dew point is difficult and stable operation is difficult. In addition, when annealing was performed under unstable dew point control, variations were observed in the distribution of internal oxides formed on the steel sheet, and chemical conversion treatment unevenness in the longitudinal and width directions of the steel sheet (overall) Or there is a concern that a part of the scale may occur. Furthermore, even when the chemical conversion treatment performance is improved, there is a problem that the corrosion resistance after electrodeposition coating is poor because the Si-containing oxide exists immediately below the chemical conversion treatment film. A method is described in which the steel sheet temperature reaches 350 to 650 ° C. to form an oxide film on the steel sheet surface, and then heated and cooled to the recrystallization temperature in a reducing atmosphere. However, in this method, there is a difference in the thickness of the oxide film formed on the surface of the steel sheet due to the oxidation method, and sufficient oxidation does not occur, or the oxide film becomes too thick, and in subsequent annealing in a reducing atmosphere. Oxide film may remain or peel off, and surface properties may deteriorate. In the examples, a technique for oxidizing in the air is described, but oxidation in the air generates a thick oxide and subsequent reduction is difficult, or a reducing atmosphere with a high hydrogen concentration is required. There are problems such as.

Furthermore, in Patent Document 6, a cold-rolled steel sheet containing 0.1% or more by mass and / or 1.0% or more of Mn by mass%, the surface of the steel sheet in an iron oxidizing atmosphere at a steel sheet temperature of 400 ° C. or more. Describes a method in which an oxide film is formed, and then the oxide film on the surface of the steel sheet is reduced in an iron reducing atmosphere. Specifically, after oxidizing Fe on the surface of the steel sheet using a direct fire burner at 400 ° C. or higher and an air ratio of 0.93 or higher and 1.10 or lower, annealing is performed in an N ₂ + H ₂ gas atmosphere that reduces Fe oxide. In this method, selective surface oxidation that degrades the chemical conversion property is suppressed, and an Fe oxide layer is formed on the outermost surface. Patent Document 6 does not specifically describe the heating temperature of an open flame burner, but when it contains a large amount of Si (approximately 0.6% or more), the amount of oxidation of Si that is easier to oxidize than Fe. As a result, the oxidation of Fe is suppressed, and the oxidation of Fe itself becomes too small. As a result, the formation of the surface Fe reduction layer after reduction may be insufficient, or SiO ₂ may be present on the steel sheet surface after reduction, resulting in the occurrence of a conversion coating.

JP-A-5-320952 JP 2004-323969 A Japanese Patent Application Laid-Open No. 6-10096 JP 2003-113441 A JP 55-145122 A JP 2006-45615 A

  The present invention has been made in view of such circumstances, and provides a high-strength steel sheet having excellent chemical conversion property and corrosion resistance after electrodeposition coating even when the content of Si and Mn is large, and a method for producing the same The purpose is to do.

  Conventionally, the inside of the steel sheet was excessively oxidized by increasing the dew point or the oxygen concentration by simply increasing the partial pressure of water vapor or oxygen in the entire annealing furnace. Therefore, various problems have occurred, such as problems in controllability, unevenness in chemical conversion treatment, and deterioration in corrosion resistance after electrodeposition coating. Therefore, the present inventors have studied a method for solving the problem by a new method not confined to the conventional idea. As a result, high strength with excellent chemical conversion treatment and corrosion resistance after electrodeposition coating by controlling the structure and structure of the steel sheet surface layer that may become the starting point of corrosion resistance degradation after electrodeposition coating It has been found that a steel plate can be obtained. Specifically, the maximum reached temperature of the steel plate in the annealing furnace is 600 ° C. or more and 750 ° C. or less, and the steel plate passage time in the temperature range of 600 ° C. or more and 750 ° C. or less is 30 seconds or more and 10 minutes or less. Continuous annealing is performed by controlling the dew point to be -10 ° C or higher. By performing such treatment, selective surface oxidation can be suppressed, surface concentration can be suppressed, and a high-strength steel sheet excellent in chemical conversion treatment properties and corrosion resistance after electrodeposition coating can be obtained. In addition, having excellent chemical conversion property means having a non-scaling and uneven appearance after chemical conversion treatment.

And the high-strength steel plate obtained by the above method is Fe, Si, Mn, Al, P, B, Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb on the steel plate surface layer portion within 100 μm from the steel plate surface. , Ta, W, V, a total of at least one oxide selected from 0.010 to 0.100 g / m ² per side, and in a region within 10 μm from the steel plate surface, It has a structure and structure in which an oxide containing Mn is present in grains within 1 μm from the grain boundary. As a result, it is possible to prevent deterioration of the corrosion resistance after electrodeposition coating, and the chemical conversion processability is excellent.

The present invention is based on the above findings, and features are as follows.
[1] By mass%, C: 0.03 to 0.35%, Si: 0.01 to 0.50%, Mn: 3.6 to 8.0%, Al: 0.01 to 1.0% , P ≦ 0.10%, S ≦ 0.010%, and when the steel sheet comprising the balance Fe and inevitable impurities is continuously annealed, the maximum temperature reached in the annealing furnace is 600 ° C. or higher and 750 ° C. The method for producing a high-strength steel sheet, characterized in that the steel sheet temperature in the temperature range of 600 ° C. to 750 ° C. is 30 seconds or more and 10 minutes or less, and the dew point in the atmosphere is −10 ° C. or more. .
[2] In the above [1], the steel sheet is in mass% as a component composition, and further B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005. -0.05%, Cr: 0.001-1.0%, Mo: 0.05-1.0%, Cu: 0.05-1.0%, Ni: 0.05-1.0%, Sn: 0.001 to 0.20%, Sb: 0.001 to 0.20%, Ta: 0.001 to 0.10%, W: 0.001 to 0.10%, V: 0.001 A method for producing a high-strength steel sheet, comprising one or more elements selected from 0.10%.
[3] The method for producing a high-strength steel sheet according to [1] or [2], further comprising performing electrolytic pickling in an aqueous solution containing sulfuric acid.
[4] Manufactured by any one of the production methods described in [1] to [3] above, Fe, Si, Mn, Al, P, B, Nb, Ti, Cr are formed on the steel sheet surface layer within 100 μm from the steel sheet surface. A total of at least one oxide selected from Mo, Cu, Ni, Sn, Sb, Ta, W, and V is formed from 0.010 to 0.100 g / m ² per side. A high-strength steel sheet characterized in that an oxide containing Mn is present in grains within 1 μm from the grain boundary of the steel sheet in a region within 10 μm from the surface.

  In the present invention, the high strength steel plate is a steel plate having a tensile strength TS of 590 MPa or more. The high-strength steel sheet of the present invention includes both cold-rolled steel sheets and hot-rolled steel sheets.

  According to the present invention, a high-strength steel sheet having excellent chemical conversion property and corrosion resistance after electrodeposition coating can be obtained even when the content of Si or Mn is large.

Hereinafter, the present invention will be specifically described. In the following description, the unit of the content of each element of the steel component composition is “mass%”, and hereinafter, simply indicated by “%” unless otherwise specified.
First, annealing atmosphere conditions that determine the structure of the steel sheet surface, which is the most important requirement in the present invention, will be described. When annealing, the steel plate maximum temperature in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower, the steel plate passage time in the temperature range of 600 ° C. or higher and 750 ° C. or lower is 30 seconds or longer and within 10 minutes, and the dew point in the atmosphere Is controlled to be −10 ° C. or higher so that an appropriate amount of an oxide of an easily oxidizable element (Si, Mn, etc.) (hereinafter referred to as an internal oxide) is present in the steel sheet surface within 100 μm, and after annealing. It is possible to suppress selective surface oxidation (hereinafter referred to as surface concentration) in the steel sheet surface layer such as Si and Mn in the steel, which deteriorates the chemical conversion property.

  The reason why the maximum temperature of the steel sheet in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower is as follows. In the temperature range below 600 ° C., surface concentration and internal oxidation to such an extent that deterioration of chemical conversion properties becomes a problem do not occur. Moreover, if it is less than 600 degreeC, a favorable material cannot be obtained. Therefore, the temperature range in which the effects of the present invention are manifested is 600 ° C. or higher. On the other hand, in the temperature range exceeding 750 ° C., the surface concentration becomes remarkable and the chemical conversion treatment property deteriorates. Furthermore, from the viewpoint of the material, the effect of balance between strength and ductility is saturated in a temperature range exceeding 750 ° C. From the above, the maximum temperature reached by the steel sheet is set to 600 ° C. or higher and 750 ° C. or lower.

Next, the reason why the steel plate passage time in the temperature range of 600 ° C. or more and 750 ° C. or less is 30 seconds or more and 10 minutes or less is as follows. If it is less than 30 seconds, the target material (TS, El) cannot be obtained. On the other hand, if it exceeds 10 minutes, the effect of balance between strength and ductility is saturated.
The reason why the dew point in the atmosphere in the temperature range where the steel sheet temperature is 600 ° C. or higher and 750 ° C. or lower is −10 ° C. or higher is as follows. By increasing the dew point, it is possible to increase the O ₂ potential resulting from the decomposition of H ₂ O and promote internal oxidation. By forming internal oxidation, a region (hereinafter referred to as a deficient layer) in which the amount of solid oxidizable elements (Si, Mn, etc.) within the surface of the steel sheet within 10 μm is reduced is formed. Suppresses surface diffusion of easily oxidizable elements. In order to form this internal oxidation and to form a deficient layer sufficient to suppress surface concentration, the dew point in the temperature range of 600 ° C. or higher and 750 ° C. or lower needs to be −10 ° C. or higher. When the temperature is lower than −10 ° C., internal oxidation is not sufficiently formed. On the other hand, the upper limit of the dew point is not particularly defined, but if it exceeds 60 ° C., the oxidation amount of Fe increases, and there is a concern about deterioration in the annealing furnace or roll, so 60 ° C. or less is desirable.

Next, the steel component composition of the high-strength steel sheet that is the subject of the present invention will be described.
C: 0.03-0.35%
C improves workability by forming martensite or the like as a steel structure. For that purpose, 0.03% or more is necessary. On the other hand, if it exceeds 0.35%, the weldability deteriorates. Therefore, the C content is 0.03% or more and 0.35% or less.

Si: 0.01 to 0.50%
Si is an element effective for strengthening steel to obtain a good material, but it is an easily oxidizable element, which is disadvantageous for chemical conversion treatment and should be avoided as much as possible. However, about 0.01% is inevitably contained in the steel, and in order to reduce to less than this, the cost increases, so 0.01% is made the lower limit. On the other hand, if it exceeds 0.50%, the steel strengthening ability and the effect of improving elongation become saturated. Moreover, chemical conversion processability deteriorates. Therefore, the Si amount is set to 0.01% or more and 0.50% or less.

Mn: 3.6-8.0%
Mn is an element effective for increasing the strength of steel. In order to ensure mechanical properties and strength, it is necessary to contain 3.6% or more. On the other hand, if it exceeds 8.0%, it will be difficult to ensure chemical conversion treatment and to ensure a balance between strength and ductility. Further, it is disadvantageous in terms of cost. Therefore, the Mn content is 3.6% or more and 8.0% or less.

Al: 0.01 to 1.0%
Al is added for the purpose of deoxidizing molten steel, but if the content is less than 0.01%, the purpose is not achieved. The effect of deoxidation of molten steel is obtained at 0.01% or more. On the other hand, if it exceeds 1.0%, the cost increases. Furthermore, the surface concentration of Al increases and it becomes difficult to improve chemical conversion properties. Therefore, the Al content is set to 0.01% to 1.0%.

P ≦ 0.10%
P is one of the elements inevitably contained, and in order to make it less than 0.005%, there is a concern about an increase in cost, so 0.005% or more is desirable. On the other hand, if P exceeds 0.10%, weldability deteriorates. Furthermore, the chemical conversion processability deteriorates, and even with the present invention, it is difficult to improve the chemical conversion processability. Accordingly, the P content is preferably 0.10% or less, and the lower limit is preferably 0.005%.

S ≦ 0.010%
S is one of the elements inevitably contained. The lower limit is not specified, but if it is contained in a large amount, the weldability and corrosion resistance deteriorate, so the content is made 0.010% or less.

In order to further improve the surface quality and balance between strength and ductility, B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005 to 0.05% Cr: 0.001-1.0%, Mo: 0.05-1.0%, Cu: 0.05-1.0%, Ni: 0.05-1.0%, Sn: 0.001 -0.20%, Sb: 0.001-0.20%, Ta: 0.001-0.10%, W: 0.001-0.10%, V: 0.001-0.10% One or more elements selected from the above may be added as necessary.
The reason for limiting the appropriate addition amount in the case of adding these elements is as follows.

B: 0.001 to 0.005%
When B is less than 0.001%, it is difficult to obtain an effect of promoting quenching. On the other hand, if it exceeds 0.005%, chemical conversion processability deteriorates. Therefore, when it contains, B amount shall be 0.001% or more and 0.005% or less. However, when it is judged that it is not necessary to improve the mechanical properties, it is not necessary to add it.

Nb: 0.005 to 0.05%
If Nb is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, the cost increases. Therefore, when it contains, Nb amount shall be 0.005% or more and 0.05% or less.

Ti: 0.005 to 0.05%
If Ti is less than 0.005%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 0.05%, chemical conversion processability is deteriorated. Therefore, when it contains, Ti amount shall be 0.005% or more and 0.05% or less.

Cr: 0.001 to 1.0%
When Cr is less than 0.001%, it is difficult to obtain a hardenability effect. On the other hand, if it exceeds 1.0%, the surface of Cr is concentrated, so that the weldability is deteriorated. Therefore, when it contains, Cr amount shall be 0.001% or more and 1.0% or less.

Mo: 0.05-1.0%
If Mo is less than 0.05%, the effect of adjusting the strength is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Mo content is 0.05% or more and 1.0% or less.

Cu: 0.05 to 1.0%
If Cu is less than 0.05%, it is difficult to obtain the effect of promoting the formation of the residual γ phase. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when contained, the Cu content is 0.05% or more and 1.0% or less.

Ni: 0.05-1.0%
If Ni is less than 0.05%, the effect of promoting the formation of residual γ phase is difficult to obtain. On the other hand, if it exceeds 1.0%, cost increases. Therefore, when it contains, Ni amount shall be 0.05% or more and 1.0% or less.

Sn: 0.001 to 0.20%, Sb: 0.001 to 0.20%
Sn or Sb can be contained from the viewpoint of suppressing decarburization in the region of several tens of microns on the surface of the steel sheet caused by nitriding, oxidation, or oxidation of the steel sheet surface. By suppressing nitriding and oxidation, it is possible to prevent a reduction in the amount of martensite produced on the surface of the steel sheet and improve fatigue characteristics and surface quality. From the above viewpoint, when Sn and / or Sb are contained, both are 0.001% or more. Moreover, since the deterioration of toughness will be caused when either content exceeds 0.20%, it is preferable to set it as 0.20% or less.

Ta: 0.001 to 0.10%
Ta contributes to high strength by forming carbides and carbonitrides with C and N, and further contributes to high yield ratio (YR). Furthermore, Ta has the effect of refining the hot-rolled sheet structure, and this effect refines the ferrite grain size after cold rolling and annealing. And the amount of C segregation to the grain boundary accompanying the increase in grain boundary area increases, and a high seizure hardening amount (BH amount) can be obtained. From such a viewpoint, Ta can be contained in an amount of 0.001% or more. On the other hand, the inclusion of excess Ta exceeding 0.10% not only increases the raw material cost, but may hinder the formation of martensite in the cooling process after annealing. Furthermore, TaC precipitated in the hot-rolled sheet increases the deformation resistance during cold rolling, and may make it difficult to manufacture a stable actual machine. Therefore, when it contains Ta, it is 0.10% or less.

W: 0.001-0.10%, V: 0.001-0.10%
W and V are elements that form carbonitrides and have the effect of increasing the strength of steel by precipitation effects, and can be added as necessary. Such an effect is recognized by adding 0.001% or more in both cases when adding W and / or V. On the other hand, when it contains exceeding 0.10%, it will become high strength too much and ductility will deteriorate. As mentioned above, when it contains W and / or V, all are 0.001% or more and 0.10% or less.

  The balance other than the above is Fe and inevitable impurities. Even if elements other than the elements described above are contained, the present invention is not adversely affected, and the upper limit is made 0.10%.

  Next, the manufacturing method of the high strength steel plate of the present invention and the reason for limitation will be described.

  After the steel having the above chemical components is hot-rolled, it is cold-rolled to obtain a steel plate, and then annealed in a continuous annealing facility. Furthermore, it is preferable to perform electrolytic pickling in an aqueous solution containing sulfuric acid. Next, chemical conversion treatment is performed. In the above, after the hot rolling, annealing may be performed as it is without performing cold rolling.

  At this time, in the present invention, the maximum reached temperature of the steel plate in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower, and the steel plate passage time in the temperature range of 600 ° C. or higher and 750 ° C. or lower is 30 seconds or longer and 10 ° Within a minute, the dew point in the atmosphere is -10 ° C or higher. This is the most important requirement in the present invention. In this way, by controlling the dew point, that is, the oxygen partial pressure in the atmosphere in the annealing process, the oxygen potential is increased and the easily oxidizable elements such as Si and Mn are internally oxidized in advance immediately before the chemical conversion treatment, and Si and Mn in the steel sheet surface layer portion. The activity of is reduced. And external oxidation of these elements is suppressed, and as a result, chemical conversion property improves.

Hot rolling Usually, it can be performed on the conditions performed.

It is preferable to perform a pickling treatment after hot pickling. The black scale formed on the surface in the pickling process is removed, and then cold-rolled. The pickling conditions are not particularly limited.

Cold rolling is preferably performed at a rolling reduction of 40% to 80%. If the rolling reduction is less than 40%, the recrystallization temperature is lowered, and the mechanical characteristics are likely to deteriorate. On the other hand, if the rolling reduction exceeds 80%, the steel sheet is a high-strength steel plate, so that not only the rolling cost is increased, but also the surface concentration during annealing is increased, so that the chemical conversion property may be deteriorated.

  A cold-rolled steel plate or a hot-rolled steel plate is subjected to continuous annealing and then subjected to chemical conversion treatment.

  In the annealing furnace, a heating process is performed in which the steel sheet is heated to a predetermined temperature in a preceding heating zone, and a soaking process is performed in which the temperature is maintained at a predetermined temperature for a predetermined time in a subsequent soaking zone. Next, a cooling process is performed.

  And as above-mentioned, the steel plate highest ultimate temperature in an annealing furnace is 600 degreeC or more and 750 degrees C or less, and the steel plate passage time in the temperature range whose steel plate temperature is 600 degreeC or more and 750 degrees C or less is 30 second or more and less than 10 minutes, The dew point in the atmosphere is −10 ° C. or higher. The dew point in the annealing furnace atmosphere other than the temperature range of 600 ° C. or higher and 750 ° C. or lower is not particularly limited. Preferably it is -50 degreeC--10 degreeC.

The gaseous components in the annealing furnace consist of nitrogen, hydrogen and unavoidable impurities. When the hydrogen concentration is less than 1 vol%, the activation effect due to the reduction cannot be obtained, and the chemical conversion treatment property may be deteriorated. The upper limit is not particularly specified, but if it exceeds 50 vol%, the cost increases and the effect is saturated. Therefore, the hydrogen concentration is preferably 1 vol% or more and 50 vol% or less. Furthermore, 5 vol% or more and 30 vol% or less are desirable. The balance consists of nitrogen and unavoidable impurity gases. Other gas components such as H ₂ O, CO ₂ and CO may be contained as long as the effects of the present invention are not impaired.
Further, when compared under the same annealing conditions, the surface enrichment amount of Si and Mn increases in proportion to the amount of Si and Mn in the steel. In the case of the same steel type, in a relatively high oxygen potential atmosphere, since Si and Mn in the steel move to internal oxidation, the amount of surface concentration decreases as the oxygen potential in the atmosphere increases. Therefore, when the amount of Si and Mn in steel is large, it is necessary to increase the oxygen potential in the atmosphere by increasing the dew point.

  Furthermore, after cooling from a temperature range of 600 ° C. to 750 ° C., quenching and tempering may be performed as necessary. The conditions are not particularly limited, but tempering is desirably performed at a temperature of 150 to 400 ° C. This is because the elongation tends to deteriorate when the temperature is less than 150 ° C., and the hardness tends to decrease when the temperature exceeds 400 ° C.

  In the present invention, good chemical conversion treatment can be ensured without carrying out electrolytic pickling, but a small amount of surface condensate inevitably generated during annealing is removed to ensure better chemical conversion treatment. For the purpose, it is preferable to perform electrolytic pickling in an aqueous solution containing sulfuric acid after continuous annealing.

  The pickling solution used for electrolytic pickling is not particularly limited, but nitric acid and hydrofluoric acid are not preferable because they are highly corrosive to equipment and require careful handling. Hydrochloric acid is not preferred because it may generate chlorine gas from the cathode. For this reason, use of sulfuric acid is preferable in consideration of corrosivity and environment. The sulfuric acid concentration is preferably 5% by mass or more and 20% by mass or less. If the sulfuric acid concentration is less than 5% by mass, the electrical conductivity will be low, so that the bath voltage during electrolysis will rise and the power load may become large. On the other hand, if it exceeds 20% by mass, a loss due to drag-out is large, which causes a problem in cost.

The conditions for the electrolytic pickling are not particularly limited, but in order to efficiently remove the inevitably surface-enriched Si and Mn oxides formed after annealing, an alternating electrolysis with a current density of 1 A / dm ² or more is used. It is desirable. The reason for alternating electrolysis is that the pickling effect is small when the steel plate is held at the cathode, and conversely, Fe that is eluted during electrolysis accumulates in the pickling solution while the steel plate is held at the anode. This is because if the Fe concentration increases and adheres to the surface of the steel sheet, problems such as dry dirt occur.

  The temperature of the electrolytic solution is preferably 40 ° C. or higher and 70 ° C. or lower. Since the bath temperature rises due to heat generated by continuous electrolysis, it may be difficult to maintain the temperature below 40 ° C. Moreover, it is not preferable that temperature exceeds 70 degreeC from a durable viewpoint of the lining of an electrolytic cell. In addition, since it is less than 40 degreeC, the pickling effect becomes small, 40 degreeC or more is preferable.

As described above, the high-strength steel sheet of the present invention is obtained. And it has the characteristic in the structure of the steel plate surface as follows.
On the steel sheet surface layer within 100 μm from the steel sheet surface, Fe, Si, Mn, Al, P, B, Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb, Ta, W, V One or more oxides selected from the group consisting of 0.010 to 0.100 g / m ² per side in total are formed. Further, in the region from the steel sheet surface to 10 μm, an oxide containing Mn exists in the grains within 1 μm from the grain boundary.

In a high-strength steel sheet with Si and a large amount of Mn added to the steel, in order to satisfy the corrosion resistance after electrodeposition coating, the structure and structure of the steel sheet surface layer, which may be the starting point of corrosion cracking, is improved. Need to control. Therefore, in the present invention, first, the dew point control is performed as described above in order to increase the oxygen potential in the annealing process in order to ensure chemical conversion treatment. As a result, by increasing the oxygen potential, easily oxidizable elements such as Si and Mn are internally oxidized in advance immediately before the chemical conversion treatment, and the activities of Si and Mn in the steel sheet surface layer portion are lowered. And external oxidation of these elements is suppressed, and as a result, chemical conversion property and corrosion resistance after electrodeposition coating are improved. Furthermore, this improvement effect is obtained by applying Fe, Si, Mn, Al, P, and B, Nb, Ti, Cr, Mo, Cu, Ni, Sn, Sb, Ta, At least one oxide selected from W and V is present in a total amount of 0.010 g / m ² or more per side. On the other hand, since this effect is saturated even if it exceeds 0.100 g / m ² , the upper limit is made 0.100 g / m ² .

  Moreover, when an internal oxide exists only in a grain boundary and does not exist in a grain, the grain boundary diffusion of an easily oxidizable element in steel can be suppressed, but the intragranular diffusion may not be sufficiently suppressed. Therefore, in the present invention, as described above, the maximum steel plate temperature in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower, and the steel plate passage time in the temperature range of 600 ° C. or higher and 750 ° C. or lower is 30 seconds or longer and 10 minutes. By controlling the dew point in the atmosphere to be −10 ° C. or higher, internal oxidation is performed not only at the grain boundaries but also within the grains. Specifically, in the region from the steel plate surface to 10 μm, an oxide containing Mn is present in grains within 1 μm from the steel plate crystal grain boundary. The presence of oxide in the grains reduces the amount of solid solution Si and Mn in the grains near the oxide. As a result, concentration on the surface due to intragranular diffusion of Si and Mn can be suppressed.

  The structure of the steel sheet surface of the high-strength steel sheet obtained by the production method of the present invention is as described above. For example, there is no problem even if the oxide grows in a region exceeding 100 μm from the steel sheet surface. . In addition, in the region exceeding 10 μm from the steel plate surface, there is no problem even if an oxide containing Mn is present in the grains of 1 μm or more from the grain boundary.

  Furthermore, in addition to the above, in the present invention, the steel sheet structure on which the oxide containing Mn grows is preferably a soft and rich ferrite phase.

Hereinafter, the present invention will be specifically described based on examples.
After pickling the hot-rolled steel sheet having the steel composition shown in Table 1 and removing the black scale, it is cold-rolled under the conditions shown in Tables 2 and 3 to obtain a cold-rolled steel sheet having a thickness of 1.0 mm. It was. In addition, some did not implement cold rolling, but the thing with the hot-rolled steel plate (thickness 2.0mm) after black scale removal was also prepared.

  Next, the cold-rolled steel sheet obtained above was charged into a continuous annealing facility. In the annealing equipment, as shown in Tables 2 and 3, the steel plate temperature in the annealing furnace is controlled through the dew point, the steel plate passage time, and the maximum steel plate temperature in the temperature range of 600 ° C. to 750 ° C. Then, water quenching was performed and tempering was performed at 300 ° C. × 140 s. Then, it pickled by being immersed in sulfuric acid aqueous solution of 40 mass% and 5 mass%. A part of the sample was subjected to electrolytic pickling by alternating electrolysis in which the test material was in the order of 3 seconds each in the order of anode and cathode under the current density conditions shown in Table 2 to obtain the test material. The dew point in the annealing furnace other than the region where the dew point was controlled was −35 ° C. The atmospheric gas components were nitrogen gas, hydrogen gas, and inevitable impurity gas, and the dew point was controlled by absorbing and removing moisture in the atmosphere. The hydrogen concentration in the atmosphere was 10 vol%.

  TS and El were measured with respect to the specimens obtained as described above. In addition, chemical conversion properties and corrosion resistance after electrodeposition coating were investigated. In addition, the amount of oxide (internal oxidation amount) present in the steel sheet surface layer up to 100 μm immediately below the steel sheet surface layer was measured. The measurement method and evaluation criteria are shown below.

Chemical conversion treatment The chemical conversion treatment liquid (Palbond L3080 (registered trademark)) manufactured by Nippon Parkerizing Co., Ltd. was used as the chemical conversion treatment liquid, and the chemical conversion treatment was performed by the following method.
After degreasing with a degreasing liquid Fine Cleaner (registered trademark) manufactured by Nihon Parkerizing Co., Ltd., washing with water, and then adjusting the surface for 30 s with surface conditioning solution preparen Z (registered trademark) manufactured by Nihon Parkerizing Co., Ltd. After being immersed in a chemical conversion treatment solution (Palbond L3080) for 120 s, it was washed with water and dried with warm air.
The sample after the chemical conversion treatment was randomly observed with a scanning electron microscope (SEM) at a magnification of 500 times, the scale area ratio of the chemical conversion film was measured by image processing, and the following evaluation was made based on the scale area ratio. Went. ○ is an acceptable level.
○: 10% or less ×: More than 10% Corrosion resistance after electrodeposition coating A test piece having a size of 70 mm × 150 mm was cut out from the test material subjected to chemical conversion treatment obtained by the above method, and PN made by Nippon Paint Co., Ltd. Cationic electrodeposition coating (baking conditions: 170 ° C. × 20 minutes, film thickness 25 μm) was performed with −150 G (registered trademark). Thereafter, the end surface and the side not evaluated were sealed with Al tape, and a cross cut (cross angle 60 °) reaching the ground iron with a cutter knife was used as a test material.

Next, the specimen was taken out after being immersed in a 5% NaCl aqueous solution (55 ° C.) for 240 hours, washed with water and dried, and then the tape was peeled off, the peel width was measured, and the following evaluation was performed. ○ is acceptable level ○: Peeling width is less than 2.5 mm on one side ×: Peeling width is 2.5 mm or more on one side Workability is obtained by taking a JIS No. 5 tensile test piece from the sample in a 90 ° direction with respect to the rolling direction. In accordance with the provisions of JIS Z 2241, a tensile test is performed at a constant crosshead speed of 10 mm / min, and tensile strength (TS / MPa) and elongation (El /%) are measured. Good and TS × El <24000 were regarded as bad.

The amount of internal oxidation in the region of the steel sheet surface layer of up to 100 μm is measured by the “impulse furnace melting-infrared absorption method”. However, since it is necessary to subtract the amount of oxygen contained in the material (that is, the high-strength steel plate before annealing), in the present invention, the surface layer portions on both surfaces of the high-strength steel plate after continuous annealing are polished by 100 μm or more in the steel. Measure the oxygen concentration, set the measured value as the amount of oxygen OH contained in the material, measure the oxygen concentration in the steel in the entire thickness direction of the high-strength steel sheet after continuous annealing, and measure the measured value internally. The subsequent oxygen amount OI was used. The difference between OI and OH (= OI-OH) is calculated using the oxygen amount OI after internal oxidation of the high-strength steel plate thus obtained and the oxygen amount OH contained in the material, and further, single-sided unit area (i.e. 1 m ²⁾ value converted into the amount per (g / m ²⁾ as an internal oxide amount.

  The results obtained above are shown in Tables 2 and 3 together with the production conditions.

  As is clear from Tables 2 and 3, the high-strength steel sheet produced by the method of the present invention is a high-strength steel sheet containing a large amount of oxidizable elements such as Si and Mn, but it is chemically treated. It can be seen that it has excellent corrosion resistance and workability after electrodeposition coating. On the other hand, in the comparative example, any one or more of chemical conversion property, corrosion resistance after electrodeposition coating, and workability is inferior.

  The high-strength steel sheet of the present invention is excellent in chemical conversion property, corrosion resistance, and workability, and can be used as a surface-treated steel sheet for reducing the weight and strength of the automobile body itself. In addition to automobiles, the steel sheet can be applied in a wide range of fields such as home appliances and building materials as a surface-treated steel sheet provided with rust prevention properties.

Claims (4)

In mass%, C: 0.03 to 0.35%, Si: 0.01 to 0.50%, Mn: 3.6 to 8.0%, Al: 0.01 to 1.0%, P ≦ When continuously annealing a steel sheet containing 0.10%, S ≦ 0.010%, the balance being Fe and inevitable impurities,
The maximum temperature of the steel plate in the annealing furnace is 600 ° C. or higher and 750 ° C. or lower, the steel plate passage time in the temperature range of 600 ° C. or higher and 750 ° C. or lower is 30 seconds or longer and within 10 minutes, and the dew point in the atmosphere is −10 A method for producing a high-strength steel sheet, characterized in that the temperature is not lower than ° C.   The steel sheet is in mass% as a component composition, and B: 0.001 to 0.005%, Nb: 0.005 to 0.05%, Ti: 0.005 to 0.05%, Cr: 0 0.001 to 1.0%, Mo: 0.05 to 1.0%, Cu: 0.05 to 1.0%, Ni: 0.05 to 1.0%, Sn: 0.001 to 0.20 %, Sb: 0.001 to 0.20%, Ta: 0.001 to 0.10%, W: 0.001 to 0.10%, V: 0.001 to 0.10% The method for producing a high-strength steel sheet according to claim 1, comprising at least one element.   3. The method for producing a high-strength steel sheet according to claim 1, wherein after the continuous annealing, electrolytic pickling is further performed in an aqueous solution containing sulfuric acid. It manufactures with the manufacturing method in any one of Claims 1-3, and Fe, Si, Mn, Al, P, B, Nb, Ti, Cr, Mo, Cu, Ni is manufactured in the steel plate surface layer part within 100 micrometers from the steel plate surface. , Sn, Sb, Ta, W, V, a total of at least one oxide selected from 0.010 to 0.100 g / m ² per side, and a region within 10 μm from the steel sheet surface The high-strength steel sheet according to claim 1, wherein an oxide containing Mn is present in grains within 1 μm from the grain boundary of the steel sheet.