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High Strength Steel Sheet

Abstract: This high-strength steel sheet contains predetermined chemical components, the metal structure thereof comprises, in terms of area ratio, 20%-70% ferrite, 5%-40% residual austenite, 0%-30% fresh martensite, a total of 20%-75% tempered martensite and bainite, and a total of 0%-10% pearlite and cementite, the ratio of the number of residual austenite grains having an aspect ratio of 2.0 or greater with respect to the total number of residual austenite grains in a range of 1/8-3/8 of the thickness from the surface is 50% or greater, the standard deviation of the area ratio of ferrite measured in 10 locations at 50 mm intervals along the sheet width direction in positions 1/4 of the sheet thickness in a cross section that is parallel to the rolling direction and perpendicular to the surface is less than 10%, and the tensile strength of the steel sheet is 780 MPa or greater.

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Patent Information

Application #
Filing Date
13 October 2021
Publication Number
05/2022
Publication Type
INA
Invention Field
METALLURGY
Status
Email
mahua.ray@remfry.com
Parent Application
Patent Number
Legal Status
Grant Date
2025-05-30
Renewal Date

Applicants

NIPPON STEEL CORPORATION
6-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo 1008071

Inventors

1. ABUKAWA Genki
c/o NIPPON STEEL CORPORATION, 6-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo 1008071
2. SHUTO Hiroshi
c/o NIPPON STEEL CORPORATION, 6-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo 1008071

Specification

[0001]The present invention relates to a high-strength steel plate having excellent tensile strength, elongation, stretch flangeability and bendability, and excellent material stability.
 The present application claims priority based on Japanese Patent Application No. 2019-128612 filed in Japan on July 10, 2019, the contents of which are incorporated herein by reference.
Background technology
[0002]
 In recent years, further improvement in fuel efficiency of automobiles has been required from the viewpoint of greenhouse gas emission regulation accompanying global warming countermeasures. The application of high-strength steel sheets in automobile parts is expanding more and more in order to reduce the weight of the vehicle body and ensure collision safety.
[0003]
 Steel sheets used for automobile parts are required to have various workability required at the time of forming parts, such as press workability and weldability, as well as strength. Specifically, from the viewpoint of press workability, the steel sheet is often required to have excellent elongation (total elongation in a tensile test; EL) and elongation flangeability (hole expansion ratio; λ).
[0004]
 On the other hand, for high-strength steel sheets, technology for obtaining a stable material in the coil is also important. This has been a relatively simple structure for low-strength steel sheets, with a ferrite structure as the main component and a trace amount of solid-melt reinforced elements as needed to ensure strength, whereas high-strength steels have a relatively simple structure. , Low-temperature transformation structures such as bainite and martensite, and precipitates such as TiC are utilized for strength assurance, and the structure is becoming complicated. These phenomena such as transformation and precipitation are greatly affected by the temperature history, but temperature variations may inevitably occur in the manufacturing process. For example, in the manufacturing process of hot-rolled steel sheets, there is a possibility that the temperature history may vary in the width direction and the longitudinal direction, such as unevenness in how the cooling water is applied in the width direction and unevenness in the cooling rate depending on the position in the coil after winding. be. Therefore, in the production of high-strength steel sheets, a technique for stabilizing the material is required, such as using a manufacturing method that reduces these temperature histories as much as possible, or designing a material that minimizes the influence of the temperature history.
[0005]
 As a technique for improving the ductility of a high-strength steel sheet, there is a TRIP steel that utilizes the TRIP (transformation-induced plasticity) effect by leaving an austenite phase in the steel structure (see, for example, Patent Document 1). TRIP steel has higher ductility than DP steel.
 Further, Non-Patent Document 1 discloses that the elongation and hole expandability of a steel sheet are improved by using the double annealing method of annealing the steel sheet twice.
[0006]
 On the other hand, regarding the material stability, for example, in Patent Document 2, for a hot-rolled steel sheet having a tensile strength of 780 MPa or more, by controlling the addition amount of Ti and V within a certain range, fine carbides are formed during hot-rolling and winding. Has been reported as a technique for uniformly precipitating the material of the hot-rolled steel sheet and, as a result, stabilizing the material of the hot-rolled steel sheet.
Prior art literature
Patent documents
[0007]
Patent Document 1: Japanese Patent Application Laid-Open No. 2006-274418
Patent Document 2: Japanese Patent Application Laid-Open No. 2013-100574
Non-patent literature
[0008]
Non-Patent Document 1: K.K. Sugimoto et al. : ISIJ International, Effects of Second Phase Morphology on Retained Austenite Morphology and Tensile Properties in a TRIP-aided Dual-phase.
Outline of the invention
Problems to be solved by the invention
[0009]
 The present inventors conducted a search to obtain a steel sheet having both elongation and hole expandability. Since the method described in Non-Patent Document 1 performs annealing twice, there is a problem that fuel cost and the like increase as compared with the manufacturing method in which single annealing is performed. Therefore, the present inventors have performed a TRIP steel sheet by annealing a hot-rolled steel sheet in order to create a similar plate-like structure (that is, a structure having a large aspect ratio of austenite) without performing the annealing twice. I tried a manufacturing method to make it. Specifically, the present inventors have studied a manufacturing method in which a hot-rolled steel sheet is wound at a low temperature of 450 ° C. or lower and then annealed. By winding at a low temperature, the structure of the hot-rolled steel sheet can be made mainly of a low-temperature transformation structure. The present inventors considered that by annealing a hot-rolled steel sheet having a structure mainly composed of a low-temperature transformation structure, a plate-like structure can be obtained by one annealing.
 However, in the steel sheet obtained by this method, material instability occurred. Specifically, the variation in the amount of ferrite measured along the plate width direction increased, and as a result, the variation in mechanical properties increased.
[0010]
 An object of the present invention is to provide a high-strength hot-rolled steel sheet having excellent tensile strength, elongation, stretch flangeability and bendability, and excellent material stability. The material stability means that there is little variation in the tensile strength and the total elongation of each part in the steel sheet.
Means to solve problems
[0011]
(1) The high-strength steel plate according to one aspect of the present invention has C: 0.030 to 0.280%, Si: 0.50 to 2.50%, Mn: 1.00 in mass% as a chemical component. ~ 4.00%, sol. Al: 0.001 to 2.000%, P: 0.100% or less, S: 0.0200% or less, N: 0.01000% or less, O: 0.0100% or less, B: 0 to 0.010 %, Ti: 0 to 0.20%, Nb: 0 to 0.20%, V: 0 to 1.000%, Cr: 0 to 1.000%, Mo: 0 to 1.000%, Cu: 0 ~ 1.000%, Co: 0 to 1.000%, W: 0 to 1.000%, Ni: 0 to 1.000%, Ca: 0 to 0.0100%, Mg: 0 to 0.0100% , REM: 0 to 0.0100%, Zr: 0 to 0.0100%, and the balance: Fe and impurities, and the martensite has an area ratio of ferrite: 20% to 70%, residual austenite: 5% to 40%, fresh martensite: 0% to 30%, reheated martensite and bainite total: 20% to 75%, and pearlite and cementite total: 0% to 10%, 1/8 thickness from the surface In the range of 3/8 thickness, the ratio of the number of retained austenite having an aspect ratio of 2.0 or more to the total number of retained austenite is 50% or more, and the plate thickness 1 / of the cross section parallel to the rolling direction and perpendicular to the surface. At the four positions, the standard deviation of the area ratio of ferrite measured at 10 points every 50 mm along the plate width direction is less than 10%, and the tensile strength is 780 MPa or more.
(2) The high-strength steel plate according to (1) may have a standard deviation of surface roughness Ra of 0.5 μm or less at 10 positions at intervals of 50 mm in the plate width direction.
(3) The high-strength steel plate according to (1) or (2) has B: 0.001% to 0.010%, Ti: 0.01 to 0.20% in mass% as the chemical component. Nb: 0.01 to 0.20%, V: 0.005% to 1.000%, Cr: 0.005% to 1.000%, Mo: 0.005% to 1.000%, Cu: 0 .005% to 1.000%, Co: 0.005% to 1.000%, W: 0.005% to 1.000%, Ni: 0.005% to 1.000%, Ca: 0.0003 It is composed of a group consisting of% to 0.0100%, Mg: 0.0003% to 0.0100%, REM: 0.0003% to 0.0100%, and Zr: 0.0003% to 0.0100%. At least one may be contained.
The invention's effect
[0012]
 According to the above aspect, it is possible to obtain a high-strength steel plate having excellent tensile strength, elongation, stretch flangeability and bendability, and excellent material stability.
A brief description of the drawing
[0013]
[Fig. 1] Fig. 1 is a conceptual diagram showing an observation surface for evaluating a metallographic structure.
[Fig. 2] Fig. 2 is a conceptual diagram showing an observation surface for evaluating retained austenite.
[Fig. 3] Fig. 3 is a conceptual diagram showing an observation surface for evaluating the standard deviation of the area ratio of ferrite.
Embodiment for carrying out the invention
[0014]
 The present inventors have made extensive studies on the cause of impaired material stability in a steel sheet that has been annealed once. Then, the present inventors have found that the variation in the surface texture of the hot-rolled steel sheet before annealing affects the material stability of the steel sheet after annealing. The variation in the surface texture (surface roughness) of the hot-rolled steel sheet tends to be larger than that of the cold-rolled steel sheet. When the surface roughness is uneven, the unevenness of the surface roughness causes the unevenness of the emissivity in the process of raising the temperature for annealing, and the resulting temperature variation is brought to the steel sheet. As a result, the variation in the amount of ferrite increases in the annealed steel sheet. It was clarified for the first time by the findings of the present inventors that controlling the surface texture of the hot-rolled steel sheet contributes to the material stabilization of the hot-rolled annealed sheet.
 The present inventors have also found an effective hot rolling method for suppressing variations in the surface texture of a steel sheet (hot-rolled steel sheet) before annealing. The present inventors have discovered that the phenomenon in which the surface scale is pressed against the steel sheet by the hot-rolled roll during hot rolling greatly characterizes the surface texture of the steel sheet after hot rolling. In order to control the surface texture of the hot-rolled steel sheet, it is important to control the scale growth during hot rolling, which is achieved by spraying a water film on the surface of the steel sheet under specific conditions during rolling. It was found that it could be done.
[0015]
 Hereinafter, the high-strength steel plate according to the embodiment of the present invention will be described in detail. However, the present invention is not limited to the configuration disclosed in the present embodiment, and various modifications can be made without departing from the spirit of the present invention. In addition, the lower limit value and the upper limit value are included in the numerical limitation range described below. Numerical values ​​that indicate "greater than" or "less than" do not fall within the numerical range. "%" Regarding the content of each element means "mass%".
[0016]
 In the high-strength steel sheet 1 according to the present embodiment, the rolling direction RD, the plate thickness direction TD, and the plate width direction WD shown in FIGS. 1 to 3 are defined as follows. The rolling direction RD means the direction in which the steel sheet is moved by the rolling roll during rolling. The plate thickness direction TD is a direction perpendicular to the rolled surface 11 of the steel plate. The plate width direction WD is a direction perpendicular to the rolling direction RD and the plate thickness direction TD. The rolling direction RD can be easily specified based on the stretching direction of the crystal grains of the steel sheet. Therefore, the rolling direction RD can be specified even in the steel sheet cut out from the material steel sheet after rolling.
[0017]
 In the high-strength steel plate according to the present embodiment, the amount of ferrite in the metal structure and the like are specified. The metallographic structure is evaluated in a cross section 12 parallel to the rolling direction RD and perpendicular to the rolling surface 11 (see FIG. 1). Hereinafter, the cross section 12 parallel to the rolling direction RD and perpendicular to the rolling surface 11 may be simply referred to as a cross section parallel to the rolling direction RD. A detailed method for evaluating the metallographic structure will be described later.
 Further, in the high-strength steel plate according to the present embodiment, the ratio of the number of retained austenites having an aspect ratio of 2.0 or more to the total number of retained austenites is defined. Retained austenite is evaluated in a cross section parallel to the rolling direction RD and the plate thickness direction TD (see FIG. 2). A detailed method for evaluating retained austenite will be described later.
[0018]
 Further, in the high-strength steel plate according to the present embodiment, the standard deviation of the area ratio of ferrite is defined. The area ratio of ferrite is measured at the plate thickness 1/4 position 121 of the cross section 12 parallel to the rolling direction RD and perpendicular to the rolling surface 11 (see FIG. 3). Ten cross sections 12 parallel to the rolling direction RD and perpendicular to the rolling surface 11 were created at intervals of 50 mm along the plate width direction WD, and the standard deviation of the area ratio of 10 ferrites measured on these surfaces is the present. It is considered to be the standard deviation of the area ratio of the ferrite according to the embodiment.
[0019]
 The plate thickness 1/4 position is a position at a depth of 1/4 of the thickness of the steel plate 1 from the rolled surface 11 of the steel plate 1. In FIGS. 1 and 2, only the position at a depth of 1/4 of the thickness of the steel plate 1 from the rolled surface 11 on the upper side of the steel plate 1 is shown as the plate thickness 1/4 position. However, as a matter of course, the position of 1/4 of the thickness of the steel plate 1 from the rolled surface 11 on the lower side of the steel plate 1 can also be treated as the position of 1/4 of the plate thickness. Further, in FIG. 3, only a part of the 10 measurement planes is shown. Further, FIG. 3 merely conceptually shows the measurement points of the area ratio of ferrite, and it is not necessary to form the measurement surface of the number density as shown in FIG. 3 as long as a predetermined requirement is satisfied. A detailed evaluation method of the standard deviation of the area ratio of ferrite will be described later.
[0020]
 [High-strength steel plate] The high-strength steel plate according
 to the present embodiment has
 C: 0.030 to 0.280%,
 Si: 0.50 to 2.50%,
 Mn: 1.00 in mass% as a chemical component. ~ 4.00%,
 sol. Al: 0.001 to 2.000%,
 P: 0.100% or less,
 S: 0.0200% or less,
 N: 0.01000% or less,
 O: 0.0100% or less,
 B: 0 to 0.010 %,
 Ti: 0 to 0.20%,
 Nb: 0 to 0.20%,
 V: 0 to 1.000%,
 Cr: 0 to 1.000%,
 Mo: 0 to 1.000%,
 Cu: 0 ~ 1.000%,
 Co: 0 to 1.000%,
 W: 0 to 1.000%,
 Ni: 0 to 1.000%,
 Ca: 0 to 0.0100%,
 Mg: 0 to 0.0100% ,
 REM: 0-0.0100%,
 Zr: 0-0.0100% or less, and
 balance: Fe and impurities
In terms
 of area ratio,
  ferrite: 20% to 70%,
  retained austenite: 5% to 40%,
  fresh martensite: 0% to 30%,
  tempered martensite and bainite total: 20% to 75% and
  total of pearlite and cementite: 0% to 10%  , with an aspect ratio of 2.0 or more to the total number of retained austenite in the range of 1/8 to 3/8 thickness from
the surface. The
number ratio is 50% or more, and
 the area ratio of ferrite measured at 10 points every 50 mm along the plate width direction at the plate thickness 1/4 position of the cross section parallel to the rolling direction and perpendicular to the surface. The standard deviation is less than 10% and the
 tensile strength is 780 MPa or more.
[0021]
1. 1. Chemical
 composition The composition of the high-strength steel sheet according to this embodiment will be described in detail below. The high-strength steel sheet according to the present embodiment contains basic elements as chemical components, and if necessary, selective elements, and the balance is Fe and impurities.
[0022]
(C: 0.030% or more and 0.280% or less)
 C is an important element for ensuring the strength of the steel sheet. If the C content is less than 0.030%, the tensile strength of 780 MPa or more cannot be secured. Therefore, the C content is 0.030% or more, preferably 0.050% or more, 0.100% or more, 0.120% or more, or 0.140% or more.
[0023]
 On the other hand, if the C content exceeds 0.280%, the weldability deteriorates, so the upper limit is set to 0.280%. The C content is preferably 0.260% or less or 0.250% or less, more preferably 0.200% or less, 0.180% or less, or 0.160% or less.
[0024]
(Si: 0.50% or more and 2.50% or less)
 Si is an important element for suppressing the precipitation of iron-based carbides and stabilizing the residual γ. If the Si content is less than 0.50%, it is difficult to obtain residual γ of 5% or more and the elongation deteriorates. Therefore, the Si content is set to 0.50% or more. The Si content is preferably 0.80% or more, 1.00% or more, or 1.20% or more.
[0025]
 On the other hand, if the Si content is more than 2.50%, the surface texture is deteriorated, so the Si content is set to 2.50% or less. The Si content is preferably 2.00% or less, more preferably 1.80% or less, 1.50% or less, or 1.30% or less.
[0026]
(Mn: 1.00% or more and 4.00% or less)
 Mn is an effective element for increasing the mechanical strength of a steel sheet. If the Mn content is less than 1.00%, it is not possible to secure a tensile strength of 780 MPa or more. Therefore, the Mn content is set to 1.00% or more. The Mn content is preferably 1.50% or more, more preferably 1.80% or more, 2.00% or more, or 2.20% or more.
[0027]
 On the other hand, if Mn is added in an excessive amount, the structure becomes non-uniform due to Mn segregation, and the bending workability is lowered. Therefore, the Mn content is 4.00% or less, preferably 3.00% or less, more preferably 2.80% or less, 2.60% or less, or 2.50% or less.
[0028]
(Sol.Al: 0.001% or more and 2.000% or less)
 Al is an element having an action of deoxidizing steel to make a steel sheet sound. sol. If the Al content is less than 0.001%, it cannot be sufficiently deoxidized. The Al content is 0.001% or more. However, when deoxidation is sufficiently required, it is more desirable to add 0.010% or more. More preferably, sol. The Al content is 0.020% or more, 0.030% or more, or 0.050% or more.
[0029]
 On the other hand, sol. When the Al content exceeds 2.000%, the weldability is remarkably lowered, and the oxide-based inclusions are increased, so that the surface texture is remarkably deteriorated. Therefore, sol. The Al content is 2.000% or less, preferably 1.500% or less, more preferably 1.000% or less, or 0.700% or less, and most preferably 0.090% or less, 0. It shall be 080% or less, or 0.070% or less. In addition, sol. Al means an acid-soluble Al that is not an oxide such as Al 2 O 3 and is soluble in an acid.
[0030]
 The high-strength steel plate according to this embodiment contains impurities as a chemical component. The term "impurity" refers to, for example, a substance mixed from ore or scrap as a raw material, or from a manufacturing environment, etc., when steel is industrially manufactured. Impurities mean, for example, elements such as P, S, and N. It is preferable to limit these impurities as follows in order to fully exert the effect of the present embodiment. Further, since the content of impurities is preferably small, it is not necessary to limit the lower limit value, and the lower limit value of impurities may be 0%.
[0031]
(P: 0.100% or less)
 P is an impurity generally contained in steel, but P may be positively contained because it has an effect of increasing tensile strength. However, when the P content exceeds 0.100%, the deterioration of weldability becomes remarkable. Therefore, the P content is limited to 0.100% or less. The P content is preferably limited to 0.080% or less, 0.070% or less, or 0.050% or less. In order to obtain the effect of the above action more reliably, the P content may be 0.001% or more, 0.002% or more, or 0.005% or more.
[0032]
(S: 0.0200% or less)
 S is an impurity contained in steel, and the smaller the amount, the more preferable it is from the viewpoint of weldability. When the S content exceeds 0.0200%, the weldability is significantly lowered, the precipitation amount of MnS is increased, and the low temperature toughness is lowered. Therefore, the S content is limited to 0.0200% or less. The S content is preferably limited to 0.0100% or less, more preferably 0.0080% or less, 0.0070% or less, or 0.0050% or less. From the viewpoint of desulfurization cost, the S content may be 0.0010% or more, 0.0015% or more, or 0.0020% or more.
[0033]
(N: 0.01000% or less)
 N is an impurity contained in steel, and the smaller the amount, the more preferable it is from the viewpoint of weldability. When the N content exceeds 0.01000%, the weldability is significantly deteriorated. Therefore, the N content is limited to 0.01000% or less, preferably 0.00900% or less, 0.00700% or less, or 0.00500% or less. The lower limit of the N content is not particularly limited, but for example, the N content may be 0.00005% or more, 0.00010% or more, or 0.00020% or more.
[0034]
(O: 0.0100% or less)
 O is an impurity contained in steel, and the smaller the amount, the more preferable it is from the viewpoint of weldability. When the O content exceeds 0.0100%, the weldability is significantly deteriorated. Therefore, the O content is limited to 0.0100% or less, preferably 0.0090% or less, 0.0070% or less, or 0.0050% or less. The lower limit of the O content is not particularly limited, but for example, the O content may be 0.0005% or more, 0.0008% or more, or 0.0010% or more.
[0035]
 The high-strength steel plate according to the present embodiment may contain selective elements in addition to the basic elements and impurities described above. For example, instead of a part of Fe which is the balance described above, B, Ti, Nb, V, Cr, Mo, Cu, Co, W, Ni, Ca, Mg, REM, and Zr are contained as selective elements. May be good. These selective elements may be contained according to the purpose. Therefore, it is not necessary to limit the lower limit of these selective elements, and the lower limit may be 0%. Further, even if these selective elements are contained as impurities, the above effects are not impaired.
[0036]
(B: 0% or more and 0.010% or less)
(Ti: 0% or more and 0.20% or less)
(Nb: 0% or more and 0.20% or less)
(V: 0% or more and 1.000% or less)
(Cr : 0% or more and 1.000% or less)
(Mo: 0% or more and 1.000% or less)
(Cu: 0% or more and 1.000% or less)
(Co: 0% or more and 1.000% or less)
(W: 0 % Or more and 1.000% or less)
(Ni: 0% or more and 1.000% or less)
 B, Ti, Nb, V, Cr, Mo, Cu, Co, W, and Ni all ensure stable strength. It is an effective element for this purpose. Therefore, these elements may be contained. However, even if B is contained in an amount of more than 0.010%, Ti and Nb are contained in an amount of more than 0.20%, and V, Cr, Mo, Cu, Co, W, and Ni are contained in an amount of more than 1.000%, the effect of the above action is obtained. Is prone to saturation and may be economically disadvantageous.
[0037]
 Therefore, the content of B is 0.010% or less, the content of Ti and Nb is 0.20% or less, respectively, and the content of V, Cr, Mo, Cu, Co, W and Ni is 1.0%, respectively. Below, or 1.000% or less. The content of B may be 0.008% or less, 0.007% or less, or 0.005% or less. The upper limit of the contents of Ti and Nb may be 0.18%, 0.15%, or 0.10%, respectively. The upper limit of the content of each of V, Cr, Mo, Cu, Co, W, and Ni may be 0.500% or less, 0.300% or less, or 0.100% or less.
[0038]
 In order to obtain the effect of the above action more reliably,
B: 0.001% or more, 0.002% or more, or 0.004% or more,
Ti: 0.01% or more, 0.02% or more, or 0.05% or more,
Nb: 0.01% or more, 0.02% or more, or 0.05% or more,
V: 0.005% or more, 0.008% or more, or 0.010% or more,
Cr: 0.005% or more, 0.008% or more, or 0.010% or more,
Mo: 0.005% or more, 0.008% or more, or 0.010% or more,
Cu: 0.005% or more, 0. 008% or more, or 0.010% or more,
Co: 0.005% or more, 0.008% or more, or 0.010% or more,
W: 0.005% or more, 0.008% or more, or 0.010 % Or more, and
Ni: 0.005% or more, 0.008% or more, or 0.010% or more,
and at least one of them is preferably contained.
[0039]
(Ca: 0% or more and 0.0100% or less)
(Mg: 0% or more and 0.0100% or less)
(REM: 0% or more and 0.0100% or less)
(Zr: 0% or more and 0.0100% or less)
 Ca, Mg, REM, and Zr are all elements that contribute to inclusion control, particularly fine dispersion of inclusions, and have an action of enhancing toughness. Therefore, one or more of these elements may be contained. However, if each of the elements is contained in an amount of more than 0.0100%, deterioration of the surface texture may become apparent. Therefore, the contents of Ca, Mg, REM, and Zr are preferably 0.01% or less, or 0.0100% or less, respectively. The upper limit of the content of each of Ca, Mg, REM, and Zr may be 0.0080%, 0.0050%, or 0.0030%. In order to obtain the effect of the above action more reliably, the content of at least one of these elements is preferably 0.0003% or more, 0.0005% or more, or 0.0010% or more.
[0040]
 Here, REM refers to a total of 17 elements of Sc, Y and lanthanoids, and is at least one of them. The content of the above REM means the total content of at least one of these elements. In the case of lanthanoids, they are industrially added in the form of misch metal.
[0041]
 In the high-strength steel plate according to the present embodiment, as chemical components, Ca: 0.0003% or more and 0.0100% or less, Mg: 0.0003% or more and 0.0100% or less, REM: 0. It is preferable to contain at least one of 0003% or more and 0.0100% or less, and Zr: 0.0003% or more and 0.0100% or less.
[0042]
 The above-mentioned steel composition may be measured by a general analysis method for steel. For example, the steel component may be measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrum). In addition, C and S may be measured by using the combustion-infrared absorption method, N by using the inert gas melting-heat conductivity method, and O by using the inert gas melting-non-dispersive infrared absorption method.
[0043]
 2. 2. Metallic structure
 In the high-strength steel sheet according to the present embodiment, the metallographic structure is ferrite: 20% to 70%, retained austenite: 5% to 40%, fresh martensite: 0% to 30%, tempered martensite in terms of area ratio. The total of sites and bainite: 20% to 75%, and the total of pearlite and cementite: 0% to 10%.
[0044]
(Ferrite: 20% to 70%)
 Ferrite is a relatively soft structure that contributes to molding. Having ferrite improves elongation, hole expandability, and bendability. In order to obtain this effect, it is necessary to have 20% or more of ferrite. Therefore, the area ratio of ferrite in the metal structure is set to 20% or more. The area ratio of ferrite may be 25% or more, 30% or more, or 35% or more.
 If the ferrite content exceeds 70%, it becomes difficult to increase the tensile strength to 780 MPa or more. Therefore, the area ratio of ferrite in the metal structure is set to 70% or less. The area ratio of ferrite may be 65% or less, 60% or less, or 50% or less.
[0045]
(Retained austenite: 5% -40%)
 Retained austenite is a tissue that contributes to elongation. To obtain this effect, 5% or more of retained austenite is required. Therefore, the area ratio of retained austenite in the metal structure is preferably 5% or more, preferably 8% or more, 10% or more, or 15% or more.
 In the production method according to the present embodiment, it is practically impossible to leave 40% or more of retained austenite. Therefore, the upper limit of the area ratio of retained austenite in the metal structure is 40%. The area ratio of retained austenite may be 35% or less, 30% or less, or 25% or less.
[0046]
(Fresh martensite: 0% to 30%)
 Fresh martensite is a tissue that inhibits moldability at the cost of contributing to strength. Therefore, fresh martensite does not have to be included, and its lower limit is set to 0%.
 On the other hand, in order to obtain the effect of improving the strength of fresh martensite, it is preferable to have fresh martensite at 2% or more, 5% or more, or 8% or more.
 On the other hand, if the amount of fresh martensite exceeds 30%, the elongation and the hole-spreading property are deteriorated. Therefore, the area ratio of the fresh martensite in the metal structure is set to 30% or less. The area ratio of fresh martensite is preferably 20% or less, more preferably 15% or less, or even more preferably 10% or less.
[0047]
(Total of tempered martensite and bainite: 20% -75%)
 Tempered martensite and bainite are tissues that contribute to strength. In order to obtain a tensile strength of 780 MPa or more, tempered martensite and bainite need to be 20% or more in total. Therefore, in the metal structure of the high-strength steel plate according to the present embodiment, the total area ratio of tempered martensite and bainite is 20% or more, preferably 30% or more, 40% or more, or 50% or more.
 On the other hand, it is not necessary to set an upper limit on the total amount of tempered martensite and bainite. As described above, the metallographic structure of the steel sheet according to the present embodiment contains 20% or more of ferrite and 5% or more of retained austenite, all of which may be tempered martensite and bainite. In other words, the total area ratio of tempered martensite and bainite can be up to 75%. The total area ratio of tempered martensite and bainite may be 70% or less, 60% or less, or 55% or less.
[0048]
(Total of pearlite and cementite: 0% to 10%)
 Pearlite and cementite are tissues that inhibit moldability. When the total area ratio of pearlite and cementite exceeds 10%, the moldability is significantly deteriorated, which is not preferable. Therefore, the total area ratio of pearlite and cementite shall be 10% or less in total. The total area ratio of pearlite and cementite may be 8% or less, 5% or less, or 3% or less. Since pearlite and cementite are not required to solve the problems of the present invention, the lower limit of the total area ratio is 0%. However, the total area ratio of pearlite and cementite may be 0.5% or more, 1% or more, or 2% or more.
[0049]
 Method for measuring metal structure
 Identification of bainite, tempered martensite, ferrite, pearlite, retained austenite and martensite constituting the metal structure of the high-strength steel sheet according to the above embodiment, confirmation of existence position and area fraction. Is measured by the following method.
 First, a nital reagent and a cross section disclosed in JP-A-59-219473 are used to corrode a cross section parallel to the rolling direction (that is, a cross section parallel to the rolling direction and perpendicular to the surface). Regarding the corrosion of the cross section, specifically, a solution prepared by dissolving 1 to 5 g of picric acid in 100 ml of ethanol was used as solution A, and 1 to 25 g of sodium thiosulfate and 1 to 5 g of citric acid were dissolved in 100 ml of water. The solution is solution B, and solution A and solution B are mixed at a ratio of 1: 1 to form a mixed solution, and 1.5 to 4% of nitric acid is further added and mixed with respect to the total amount of this mixed solution. The prepared liquid is used as a pretreatment liquid. Further, a liquid obtained by adding and mixing the above-mentioned pretreatment liquid at a ratio of 10% with respect to the total amount of the 2% nital liquid to the 2% nital liquid is used as a post-treatment liquid. A cross section parallel to the rolling direction (that is, a cross section parallel to the rolling direction and perpendicular to the surface) is immersed in the pretreatment solution for 3 to 15 seconds, washed with alcohol and dried, and then dipped in the posttreatment solution for 3 to 20. After soaking for a second, it is washed with water and dried to corrode the above cross section.
 Next, as shown in FIG. 1, at a depth of 1/4 of the plate thickness from the surface (rolled surface 11) of the steel plate 1 and at the center of the WD in the plate width direction, a magnification of 1000 to 1000 is used using a scanning electron microscope. By observing at least 3 regions of 40 μm × 30 μm at 100,000 times, the above-mentioned metallographic structure is identified, the existence position is confirmed, and the area fraction is measured. Even if the measurement target is a steel plate that has not been specially machined after manufacturing (in other words, a steel plate that has not been cut out from the coil) or a steel plate cut out from the coil, the center position in the plate width direction. Is a position substantially equal to both ends of the steel sheet 1 as seen in the WD in the plate width direction.
 In addition, it is difficult to distinguish between lower bainite and tempered martensite by the above-mentioned measuring method. Therefore, in this embodiment, it is not necessary to distinguish between the two. That is, the total area fraction of "bainite and tempered martensite" is obtained by measuring the area fraction of "upper bainite" and "lower bainite or tempered martensite". Upper bainite is an aggregate of laths, a structure containing carbides between the laths. The lower bainite is a structure containing iron-based carbides having a major axis of 5 nm or more and extending in the same direction inside. Tempering martensite is a collection of lath-shaped crystal grains, and is a structure containing iron-based carbides having a major axis of 5 nm or more and extending in different directions.
[0050]
 Ferrite is a region where the brightness is low and no substructure is recognized. Areas with high brightness and no underlying structure exposed by etching are judged to be fresh martensite or retained austenite. Therefore, the area fraction of fresh martensite can be obtained as the difference between the area fraction of the uncorroded region observed by FE-SEM and the area fraction of retained austenite measured by X-ray described later. can.
[0051]
 Pearlite means a region where plate-shaped cementite and plate-shaped ferrite are alternately arranged. In the observation by FE-SEM, pearlite and the above-mentioned structure (ferrite, bainitic ferrite, bainite, tempered martensite) can be clearly distinguished.
[0052]
 Methods for measuring the area fraction of retained austenite include X-ray diffraction, EBSP (Electron Backscattering Diffraction Pattern) analysis, and magnetic measurement methods, and the measured values ​​may differ depending on the measurement method. .. In this embodiment, the surface integral of retained austenite is measured by X-ray diffraction. In the measurement of the residual austenite area fraction by X-ray diffraction in the present embodiment, first, a cross section parallel to the rolling direction (that is, parallel to the rolling direction and perpendicular to the surface) at a depth position of 1/4 of the plate thickness of the steel plate is obtained. In the cross section), the integrated intensity of a total of 6 peaks of α (110), α (200), α (211), γ (111), γ (200), and γ (220) was obtained using Co—Kα rays. Then, the area fraction of retained austenite is obtained by calculation using the intensity averaging method.
[0053]
(In the range of 1/8 thickness to 3/8 thickness, the ratio of the number of retained austenites having an aspect ratio of 2.0 or more to the total retained austenite is 50% or more.
 ) It contributes to the improvement of elongation, hole expandability, and bendability, and is one of the important structure-building points in the present invention. Making the retained austenite plate-shaped has the effect of suppressing strain distribution to the austenite during molding and appropriately stabilizing the retained austenite against plastic deformation, thereby improving elongation and hole expandability. The form of retained austenite having this effect is 2.0 or more in aspect ratio.
 In order to obtain this effect, the number ratio of retained austenite having an aspect ratio of 2.0 or more in the range of 1/8 thickness to 3/8 thickness needs to be 50% or more with respect to the total retained austenite. Therefore, the number ratio is 50% or more, preferably 70% or more. If the number ratio is less than 50%, it is difficult to achieve both excellent elongation, hole expandability, and bendability, which is not preferable.
[0054]
 The aspect ratio and major axis of the retained austenite grains contained in the steel structure inside the steel sheet are evaluated by observing the crystal grains using FE-SEM and performing high-resolution crystal orientation analysis by the EBSD method (electron backscatter diffraction method). do.
 First, as shown in FIG. 2, a sample is taken with the cross section parallel to the rolling direction and the plate thickness direction of the steel plate as the observation surface 13, and the observation surface is polished to be finished as a mirror surface. Next, a total of 2.0 in one or more observation fields of the range 131 of 1/8 thickness to 3/4 thickness centered on the position of the surface (rolled surface) 11 to 1/4 thickness on the observation surface 13. Crystal structure analysis is performed by the EBSD method for an area of × 10 -9 m 2 or more (either a plurality of fields of view or the same field of view is possible). Next, in order to avoid measurement errors, only austenite having a major axis length of 0.1 μm or more is extracted from the crystal orientation of the retained austenite grains measured by the above method, and a crystal orientation map is drawn. The boundary that causes a crystal orientation difference of 10 ° or more is regarded as the grain boundary of the residual austenite grains. The aspect ratio is a value obtained by dividing the major axis length of the retained austenite grain by the minor axis length. The major axis is the major axis length of the retained austenite grains. For the analysis of the data obtained by the EBSD method in the measurement, "OIM Analysis 6.0" manufactured by TSL Co., Ltd. is used. The distance between scores (step) is 0.01 to 0.20 μm. From the observation results, the region judged to be FCC iron is defined as retained austenite. From this result, the ratio of the number of retained austenite having an aspect ratio of 2.0 or more to the total retained austenite in the range of 1/8 thickness to 3/8 thickness is obtained.
[0055]
(When the area ratio of ferrite at the plate thickness 1/4 position of the cross section parallel to the rolling direction and perpendicular to the surface is measured at 10 points every 50 mm in the plate width direction, the standard deviation of the area ratio of ferrite is 10%. Less than)
 In the present invention, ferrite is important for ensuring elongation and hole expandability. On the other hand, the strength, elongation, and hole-spreading property change depending on the tissue fraction. Therefore, it is important to obtain material stability that the structure fraction of ferrite is evenly distributed in the thermal rolling direction.
 As shown in FIG. 3, the area ratio of ferrite at the plate thickness 1/4 position 121 of the cross section parallel to the rolling direction (that is, the cross section parallel to the rolling direction and perpendicular to the surface 12) is measured in the plate width direction (that is, rolling). (Direction perpendicular to the direction RD) When measured at 10 points every 50 mm along the WD, if the standard deviation of the area ratio of ferrite is 10% or more, it causes variations in mechanical properties and material stability is obtained. No. Therefore, the standard deviation of the area ratio of the above-mentioned ferrite is set to less than 10%, preferably 8% or less, less than 5%, or 4% or less. When the size of the steel plate to be measured along the plate width direction is sufficiently large, the measurement points of the standard deviation of the area ratio of ferrite may be arranged on a straight line along the plate width direction. On the other hand, when the size of the steel plate to be measured along the plate width direction is less than 450 mm, the measurement points of the standard deviation of the area ratio of ferrite are arranged on two or more straight lines along the plate width direction. It is good to do it. When measuring the standard deviation in the plate width direction of characteristics other than ferrite (for example, surface roughness, etc.), the measurement points can be arranged as described above.
[0056]
3. 3. Standard deviation of surface roughness Ra
(standard deviation of surface roughness Ra measured at 10 points every 50 mm along the plate width direction is preferably 0.5 μm or less)
 Chemical composition, metal structure, and tensile strength described later. The steel plate according to this embodiment is not particularly limited as long as is within a predetermined range. On the other hand, when the surface roughness Ra of the rolled surface 11 is measured at 10 points every 50 mm along the plate width direction (that is, the direction perpendicular to the rolling direction), the standard deviation of the surface roughness Ra is 0.5 μm or less. May be. By suppressing the variation in the surface roughness Ra, it is possible to suppress the variation in the bending workability and further improve the material stability. Therefore, it is preferable that the standard deviation is 0.5 μm or less. However, the surface roughness of the steel sheet can be freely changed by additional machining. For example, after producing a high-strength steel plate having excellent material stability by a preferable manufacturing method described later, the high-strength steel plate may be subjected to processing such as hairline processing to change the surface roughness. From this point of view, it is not essential that the standard deviation of the surface roughness Ra is within the above range.
[0057]
 For the surface roughness Ra, a contact roughness meter (Mitutoyo surf test SJ-500) was used to acquire a roughness curve over a length of 5 mm in the plate width direction at each measurement position, and JIS B0601: 2001. The arithmetic average roughness Ra is obtained by the method described in 1. Using the value of the arithmetic mean roughness Ra at each measurement position thus obtained, the standard deviation of the surface roughness Ra is obtained.
[0058]
 When a surface treatment film such as plating or painting is arranged on the surface of the steel sheet, "surface roughness Ra of the steel sheet" means the surface roughness measured after removing the surface treatment film from the steel sheet. do. That is, the surface roughness Ra of the steel sheet is the surface roughness of the base iron. The method for removing the surface-treated film can be appropriately selected according to the type of the surface-treated film within a range that does not affect the surface roughness of the base iron. For example, when the surface-treated film is galvanized, the zinc-plated layer may be dissolved with dilute hydrochloric acid to which an inhibitor is added. As a result, only the galvanized layer can be peeled off from the steel sheet. Inhibitors are additives used to suppress changes in roughness due to prevention of overdissolution of ground iron. For example, zinc-plated hydrochloric acid diluted 10 to 100 times with the addition of Asahi Chemical Co., Ltd.'s hydrochloric acid pickling corrosion inhibitor "Ibit No. 700BK" to a concentration of 0.6 g / L. It can be used as a layer peeling means.
[0059]
4. Mechanical properties
(tensile strength TS: 780 MPa or more)
 The high-strength steel plate according to this embodiment has a tensile strength (TS) of 780 MPa or more as a sufficient strength that contributes to weight reduction of automobiles. The tensile strength of the steel sheet may be 800 MPa or more, 900 MPa or more, or 1000 MPa or more. On the other hand, it is presumed that it is difficult to make it exceed 1470 MPa in the configuration of this embodiment. Therefore, it is not necessary to set the upper limit of the tensile strength in particular, but in the present embodiment, the upper limit of the substantial tensile strength can be set to 1470 MPa. Further, the tensile strength of the steel sheet may be 1400 MPa or less, 1300 MPa or less, or 1200 MPa or less.
[0060]
 The tensile test may be performed by the following procedure in accordance with JIS Z2241 (2011). JIS No. 5 test pieces are collected from 10 positions on the high-strength steel sheet at intervals of 50 mm in the plate width direction. Here, the plate width direction of the steel plate and the longitudinal direction of the test piece are made to coincide with each other. In addition, each test piece is sampled at a position shifted in the rolling direction of the steel sheet so that the sampling positions of the test pieces do not interfere with each other. Tensile tests are carried out on these test pieces in accordance with the provisions of JIS Z 2241 (2011), the tensile strength TS (MPa) is obtained, and the average value thereof is calculated. This average value is regarded as the tensile strength of the high-strength steel sheet.
[0061]
 Further, the high-strength steel plate according to the present embodiment may have the following characteristics such as elongation and hole widening as an index of formability. These mechanical properties are obtained by the various properties of the high-strength steel sheet according to the present embodiment described above.
[0062]
(Total Elongation EL)
 The high-strength steel plate according to the present embodiment may have a total elongation of 14% or more in a tensile test as an index of elongation. On the other hand, it is difficult to make the total elongation exceed 35% in the configuration of this embodiment. Therefore, the upper limit of the substantially total growth may be 35%.
[0063]
(Drilling property)
 The high-strength steel plate according to the present embodiment may have a hole expanding rate of 25% or more as an index of the hole expanding property. On the other hand, it is difficult to make the hole expansion rate more than 80% in the configuration of the present embodiment. Therefore, the upper limit of the substantial hole expansion rate may be 80%.
 The hole expansion rate can be evaluated by a hole expansion test based on the test method described in the Japan Iron and Steel Federation standard JFS T 1001-1996.
[0064]
(Bendability)
 The high-strength steel plate according to the present embodiment has an R of 2.0 or less when a value R / t obtained by dividing the limit bending R (mm) by the plate thickness t (mm) is used as an index of bendability. It may have / t. On the other hand, it is difficult to set the bendability index R / t to 0.1 or less in the configuration of the present embodiment. Therefore, the lower limit of the substantial bendability index R / t may be set to 0.1.
 The limit bending R is obtained by repeatedly performing bending tests to which various bending radii are applied. In the bending test, bending is performed in accordance with JIS Z 2248 (V block 90 ° bending test). The bending radius (to be exact, the inner radius of the bending) is changed at a pitch of 0.5 mm. The smaller the bend radius in the bending test, the more likely it is that the steel sheet will have cracks and other defects. The minimum bending required in this test that does not cause tears and other defects in the steel sheet is regarded as the limit bending R. Then, the value obtained by dividing this limit bending R by the thickness t of the steel sheet is used as an index R / t for evaluating the bendability.
[0065]
 The high-strength steel plate according to the present embodiment has tensile test results measured at 10 points every 50 mm along the plate width direction (that is, the direction perpendicular to the rolling direction) as an index of the material stability. In, the standard deviation of TS may be 50 MPa or less, and the standard deviation of EL may be 1% or less. The method for obtaining the TS standard deviation and the EL standard deviation is the same as the above-mentioned tensile test method for obtaining the average value of the tensile strength. The TS standard deviation and the EL standard deviation can be obtained by obtaining the standard deviation of the results of 10 tensile tests by the above method.
[0066]
 Further, in the high-strength steel plate according to the present embodiment, the standard deviation of R / t (limit bending R (mm), plate thickness t (mm)) measured at 10 points every 50 mm along the plate width direction is obtained. It may be 0.2 or less.
[0067]
5. Manufacturing Method
 Next, an example of a preferable manufacturing method for the high-strength steel sheet according to the present embodiment will be described. However, it should be noted that the method for manufacturing the high-strength steel sheet according to the present embodiment is not particularly limited. All steel sheets satisfying the above requirements are considered to be the steel sheets according to the present embodiment regardless of the manufacturing method thereof.
[0068]
 The manufacturing process prior to hot rolling is not particularly limited. That is, after melting in a blast furnace, an electric furnace, or the like, various secondary smelting may be performed, and then casting may be performed by a method such as ordinary continuous casting, casting by an ingot method, or thin slab casting. In the case of continuous casting, the cast slab may be cooled to a low temperature and then heated again and then hot-rolled, or the cast slab may be hot-rolled as it is after casting without being cooled to a low temperature. good. Scrap may be used as a raw material.
[0069]
 The cast slab is heated. In this heating step, it is preferable to heat the slab to a temperature of 1100 ° C. or higher and 1300 ° C. or lower. Coarse precipitates deposited in the slab (iron-based carbides, carbonitrides of alloying elements, etc.) may impair material stability, so the slab may be heated to 1100 ° C or higher to dissolve it. preferable. On the other hand, from the viewpoint of preventing scale loss, the slab heating temperature is preferably 1300 ° C. or lower.
[0070]
 Next, the heated slab is roughly rolled to obtain a rough-rolled plate.
 In the rough rolling, the slab may have a desired size and shape, and the conditions thereof are not particularly limited. The thickness of the rough-rolled sheet affects the amount of temperature drop from the tip to the tail of the hot-rolled steel sheet from the start of rolling to the end of rolling in the finish rolling process, so it should be determined in consideration of this. Is preferable.
[0071]
 The rough-rolled plate is subjected to finish rolling. In this finish rolling process, multi-step finish rolling is performed. In this embodiment, finish rolling is performed in a temperature range of 850 ° C to 1200 ° C under the condition of satisfying the following formula (1).
 K'/ Si * ≧ 2.5 ... (1)
 Here, when Si ≧ 0.35, Si * = 140√Si, and when Si <0.35, Si * = 80. In addition, Si represents the Si content (mass%) of the steel sheet.
[0072]
 Further, K'in the above formula (1) is represented by the following formula (2).
 K'= D x (DT-930) x 1.5 + Σ ((FT n -930) x Sn ) ... (2)
 Here, D is the amount of water pressure descaling per hour before the start of finish rolling. (M 3 / min), DT is the steel sheet temperature (° C.) at the time of hydraulic descaling before the start of finish rolling, FT n is the steel sheet temperature (° C.) at the nth stage of finish rolling , and Sn is n of finish rolling. -The amount of spraying per hour (m 3 / min) when water is sprayed onto the steel sheet between the 1st stage and the nth stage .
[0073]
 Si * is a parameter related to the steel sheet component that indicates the susceptibility to unevenness due to scale. When the amount of Si in the steel sheet component is large, the scale generated on the surface layer during hot rolling grows from Wustite (FeO), which is relatively easy to descale and difficult to form unevenness on the steel sheet, and grows to form unevenness on the steel sheet. It changes to a fire light (Fe 2 SiO 4 ) that is easy to make. Therefore, the larger the amount of Si, that is, the larger the Si * , the easier it is for the surface layer to have irregularities. Here, the easiness of forming the unevenness of the surface layer by adding Si becomes particularly remarkable when 0.35% by mass or more of Si is added. Therefore, Si * becomes a function of Si when 0.35% by mass or more is added, but becomes a constant when 0.35% by mass or less.
[0074]
 K'is a parameter of manufacturing conditions indicating the difficulty of forming unevenness. The first item of the above formula (2) is that when hydraulic descaling is performed before the start of finish rolling in order to suppress the formation of unevenness, the larger the amount of hydraulic descaling per hour sprayed and the higher the steel sheet temperature. Show that it is effective from the viewpoint of descaling. When performing multiple descaling before the start of finish rolling, the descaling value closest to the finish rolling is used.
[0075]
 The second item of the above formula (2) is a section showing the effect of descaling the scale that could not be completely peeled off by descaling before finishing and the scale that was reformed during finish rolling during finish rolling. It is shown that at high temperatures, spraying a large amount of water onto the steel sheet on the spray makes it easier to descale.
[0076]
 If the ratio of the parameter K'in the manufacturing conditions, which indicates the difficulty of forming irregularities, and the parameter Si * , which indicates the ease of forming scale scratches , is 2.5 or more, or 2.50 or more, the irregularities are formed. It can be sufficiently suppressed, and temperature variation during tempering can be suppressed. Therefore, K'/ Si * is set to 2.5 or more, preferably 3.0 or more, and more preferably 3.5 or more.
[0077]
 The standard deviation of the surface roughness Ra measured at 10 positions at 50 mm intervals in the plate width direction (that is, the direction perpendicular to the rolling direction), which is a preferable form of the steel plate according to the present invention, is set to 0.5 μm or less. In order to do so, it is preferable that K'/ Si * is 3.0 or more (K'/ Si * ≧ 3.0).
[0078]
 Following finish rolling, cooling is performed at an average cooling rate of 50 ° C./s or higher, and winding is performed at a winding temperature of 450 ° C. or lower. This is because, as described above, the morphology of residual γ after annealing is controlled by using bainite and martensite, which are low-temperature transformation tissues, as the main tissues. Here, the average cooling rate is a value obtained by dividing the difference in temperature between the start of cooling and the temperature before winding by that time. If the average cooling rate is less than 50 ° C./s, ferrite transformation occurs, which hinders the control of microstructural morphology in the subsequent annealing step, and the ratio of the number of retained austenites having an aspect ratio of 2.0 or more to the total number of retained austenites is 50%. It cannot be controlled more than that.
[0079]
 Similarly, if the take-up temperature exceeds 450 ° C., ferrite transformation occurs, and it becomes difficult to make the total of bainite and tempered martensite 20% or more of the total. Further, when the winding temperature exceeds 450 ° C., the ratio of the number of retained austenites having an aspect ratio of 2.0 or more to the total number of retained austenites cannot be controlled to 50% or more. From this point of view, the winding temperature is 450 ° C. or lower, preferably 400 ° C. or lower, and more preferably 200 ° C. or lower. Further, setting the winding temperature to 450 ° C. or lower also has an effect of suppressing the formation of internal oxides on the surface of the steel sheet after winding and increasing the roughness of the surface layer.
[0080] [0080]
 The high-strength steel sheet thus produced is pickled for the purpose of removing oxides on the surface of the steel sheet. The pickling treatment may be carried out, for example, in hydrochloric acid having a concentration of 3 to 10% at a temperature of 85 ° C. to 98 ° C. for 20 seconds to 100 seconds.
[0081]
 Further, the manufactured hot-rolled steel sheet may be lightly reduced with a reduction ratio of 20% or less for the purpose of shape correction. However, when the reduction rate under light reduction exceeds 20%, recrystallization occurs in the annealing process, and the effect of morphological control obtained at the time of annealing from the low-temperature transformed structure cannot be obtained. The reduction rate shall be 20% or less. The light reduction may be carried out before or after the pickling step. Light reduction after the pickling step has the effect of further reducing the roughness of the surface layer. When the surface roughness Ra, which is a preferred embodiment in the present invention, is measured at 10 positions at intervals of 50 mm in the plate width direction (that is, the direction perpendicular to the rolling direction), the standard deviation of the surface roughness Ra is 0.5 μm. In order to satisfy the following, it is necessary to perform light rolling after the pickling step.
[0082]
 The obtained steel sheet is annealed. In the annealing step, the heating temperature is set to Acc1 point to Ac3 point −10 ° C.
 calculated by the following formula .  A c1 = 723-10.7 x Mn-16.9 x Ni + 29.1 x Si + 16.9 x Cr  A c3 = 879-346 x C + 65 x Si-18 x Mn + 54 x Al ... (9)  Low temperature transformation structure during heating Ferrite-austenite transformation occurs from the carbides formed between the laths, and plate-shaped austenite is formed. The region that did not undergo austenite transformation can be thought of as a low-temperature transformed structure (tempering martensite or tempered bainite) that has been tempered at high temperatures, but the dislocation density is greatly reduced by tempering, and the substructure is also unclear. Therefore, it is a region to be evaluated as ferrite in the microstructure observation after annealing. Therefore, it is also referred to as ferrite here. The regions evaluated as tempered martensite or bainite in the microstructure observation after annealing were generated by bainite transformation or martensitic transformation while the austenite generated by heating was held at 150 ° C to 550 ° C, which will be described later. Mainly refers to the organization.

 The reason why the heating temperature is set to Ac1 to Ac3 to −10 ° C. is to set an appropriate ferrite-austenite transformation fraction in order to set the area ratio of ferrite to 20% to 70%. The heating time is 10 seconds to 1000 seconds. If the holding time is less than 1 second, the cementite in the steel may remain undissolved and the characteristics of the steel sheet may be deteriorated. Since this effect saturates in more than 1000 seconds and leads to a decrease in productivity, the holding time is limited to 1000 seconds.
[0083]
 Then, it is held between 150 ° C. and 550 ° C. for 10 to 1000 seconds.
 In this temperature range, part of austenite is transformed into bainite or martensite, and solid-dissolved carbon is exhaled to austenite due to bainite transformation, and solid-dissolved carbon is exhaled to austenite due to tempering of martensite. , Has the effect of stabilizing austenite. At 150 ° C. or lower, most of austenite undergoes martensitic transformation, and a sufficient amount of retained austenite cannot be obtained. On the other hand, above 550 ° C., pearlite transformation occurs and retained austenite cannot be sufficiently stabilized. If the retention time is less than 10 seconds, carbon diffusion does not occur sufficiently and retained austenite cannot be sufficiently stabilized. Above 1000 seconds, the effect of stabilizing retained austenite is saturated and productivity is reduced.
[0084]
 It should be noted that while the temperature is maintained in this temperature range, heating or cooling may be performed in the temperature range. For example, once the temperature is lowered to 250 ° C. or lower to transform a part of the retained austenite into martensite, and then reheated to a temperature range of about 400 ° C., the martensite becomes a nucleation site of bainite transformation and bainite transformation. The effect of accelerating is obtained.
[0085]
 Further, hot-dip galvanizing or alloyed hot-dip galvanizing may be performed in this temperature range. General conditions can be used as the plating conditions such as the zinc plating bath temperature and the zinc plating bath composition in the hot-dip galvanizing step, and there is no particular limitation. For example, the plating bath temperature may be 420 to 500 ° C., the penetration plate temperature of the steel plate may be 420 to 500 ° C., and the immersion time may be 5 seconds or less. The plating bath is preferably a plating bath containing 0.08 to 0.2% of Al, but may also contain impurities such as Fe, Si, Mg, Mn, Cr, Ti, and Pb. Further, it is preferable to control the basis weight of the hot-dip galvanizing by a known method such as gas wiping. The basis weight is usually 5 g / m 2 or more per side, but is preferably 25 to 75 g / m 2 , and more preferably 20 to 120 g / m 2 .
 When the alloying treatment is carried out, it may be carried out according to a conventional method, but the alloying treatment temperature is preferably 460 to 550 ° C. If the alloying treatment is less than 460 ° C., not only the alloying speed becomes slow and the productivity is impaired, but also the alloying treatment unevenness occurs. Therefore, the alloying treatment temperature is preferably 460 ° C. or higher. On the other hand, when the alloying treatment temperature exceeds 550 ° C., pearlite transformation occurs and the retained austenite cannot be sufficiently stabilized.
 Further, the alloying treatment is preferably performed under the condition that the iron concentration in the hot-dip galvanized layer is 6.0% by mass or more.
 When hot-dip galvanizing or alloying hot-dip galvanizing is not performed, an electrogalvanized layer may be formed on the steel sheet manufactured as described above. The electrogalvanized layer can be formed by a conventionally known method.
[0086]
 The high-strength steel plate according to the present embodiment can be manufactured by the above-mentioned manufacturing method.
Example
[0087]
 Hereinafter, the high-strength steel plate according to the present invention will be described more specifically with reference to an example. However, the following examples are examples of the high-strength steel sheet of the present invention, and the high-strength steel sheet of the present invention is not limited to the following aspects. The conditions in the examples described below are one condition example adopted for confirming the feasibility and effect of the present invention, and the present invention is not limited to these one condition examples. The present invention can adopt various conditions as long as the gist of the present invention is not deviated and the object of the present invention is achieved.
[0088]
 Steels with the chemical components shown in Table 1 are cast, and after casting, they are heated as they are or once cooled to room temperature and then reheated to a temperature range of 1200 ° C to 1350 ° C, and then the slab is roughened at a temperature of 1100 ° C or higher. A rough-rolled plate was produced by rolling. In Table 1, values ​​outside the scope of the invention are underlined.
[0089]
[table 1]

[0090]
 The rough-rolled plate was subjected to multi-step finish rolling consisting of 7 steps in all steps under the conditions shown in Table 2.
 Then, under each condition shown in Table 3, cooling and winding after finish rolling were performed.
 After that, pickling was carried out under all conditions, but under some conditions, light reduction was carried out before or after the pickling. Then, the temperature was raised to the heating temperature shown in Table 3 at a heating rate of 30 ° C./s to 150 ° C./s. After heating, the temperature was maintained at the heating temperature for the time shown in Table 3. Then, under condition A, it was cooled to 250 ° C. at 50 to 100 ° C./s, reheated at 400 ° C., and then held for 300 seconds. Under condition B, the mixture was cooled to 360 ° C. at 50 to 100 ° C./s and held for 50 seconds. Under condition C, which is a comparative example, the mixture was cooled to 100 ° C. at 100 ° C./s and held for 300 seconds.
 After that, some conditions were alloyed hot-dip galvanized or hot-dip galvanized. In the plating process, the steel sheet was in the temperature range of 400 ° C to 520 ° C.
[0091]
[Table 2]

[0092]
[Table 3]

[0093]
 The metallographic structure of the obtained high-strength steel sheet was observed by the following method.
 First, the Nital reagent and the reagent disclosed in JP-A-59-219473 were used to corrode a cross section parallel to the rolling direction and perpendicular to the surface. Regarding the corrosion of the cross section, specifically, a solution prepared by dissolving 1 to 5 g of picric acid in 100 ml of ethanol was used as solution A, and 1 to 25 g of sodium thiosulfate and 1 to 5 g of citric acid were dissolved in 100 ml of water. The solution is solution B, and solution A and solution B are mixed at a ratio of 1: 1 to form a mixed solution, and 1.5 to 4% of nitric acid is further added and mixed with respect to the total amount of this mixed solution. The prepared liquid was used as a pretreatment liquid. Further, a liquid obtained by adding and mixing the above-mentioned pretreatment liquid at a ratio of 10% with respect to the total amount of the 2% nital liquid to the 2% nital liquid was used as a post-treatment liquid. The cross section parallel to the rolling direction and perpendicular to the surface is immersed in the pretreatment liquid for 3 to 15 seconds, washed with alcohol and dried, then immersed in the posttreatment liquid for 3 to 20 seconds, washed with water and dried. As a result, the above cross section was corroded.
[0094]
 Next, by observing at least three regions of 40 μm × 30 μm at a magnification of 1000 to 100,000 times using a scanning electron microscope at a depth of 1/4 of the plate thickness from the surface of the steel plate and at the center position in the plate width direction. The metallographic structure was identified, the location was confirmed, and the area fraction was measured.
 The total area fraction of "bainite and tempered martensite" was obtained by measuring the area fraction of "upper bainite" and "lower bainite or tempered martensite".
[0095]
 The region where the brightness was low and the substructure was not recognized was judged to be ferrite. Areas with high luminance and no underlying structure exposed by etching were judged to be fresh martensite or retained austenite. The area fraction of fresh martensite was determined as the difference between the area fraction of the uncorroded region observed by FE-SEM and the area fraction of retained austenite measured by X-ray.
[0096]
 Since pearlite can clearly distinguish between pearlite and ferrite, bainitic ferrite, bainite, and tempered martensite in observation by FE-SEM, the area ratio was determined by this method.
[0097]
 The surface integral of the retained austenite was measured by X-ray diffraction. First, α (110), α (200), α (211), α (110), α (200), α (211), using Co—Kα rays in a cross section parallel to the rolling direction and perpendicular to the surface at a depth of 1/4 of the plate thickness of the steel plate. The integrated intensities of a total of 6 peaks of γ (111), γ (200), and γ (220) were obtained and calculated using the intensity averaging method to obtain the area fraction of retained austenite.
[0098]
 The aspect ratio and major axis of the retained austenite grains contained in the steel structure inside the steel sheet are evaluated by observing the crystal grains using FE-SEM and performing high-resolution crystal orientation analysis by the EBSD method (electron backscatter diffraction method). did.
 First, a sample was taken with a cross section parallel to the rolling direction and the plate thickness direction of the steel plate as an observation surface, and the observation surface was polished to a mirror surface. Next, in one or more observation fields in the range of 1/8 to 3/8 thickness centered on the position of 1/4 thickness from the surface on the observation surface, a total of 2.0 × 10-9 m 2 or more . A crystal structure analysis was performed by the EBSD method for the area (either a plurality of fields of view or the same field of view is possible). Next, in order to avoid measurement errors, only austenite having a major axis length of 0.1 μm or more was extracted from the crystal orientation of the retained austenite grains measured by the above method, and a crystal orientation map was drawn. The boundary that causes a crystal orientation difference of 10 ° or more was regarded as the grain boundary of the residual austenite grains. The aspect ratio was the value obtained by dividing the major axis length of the retained austenite grain by the minor axis length. The major axis was the major axis length of the retained austenite grains. For the analysis of the data obtained by the EBSD method in the measurement, "OIM Analysys 6.0" manufactured by TSL was used. The distance between scores (step) was 0.01 to 0.20 μm. From the observation results, the region judged to be FCC iron was designated as retained austenite. From this result, the ratio of the number of retained austenite having an aspect ratio of 2.0 or more to the total retained austenite in the range of 1/8 thickness to 3/8 thickness was determined.
[0099]
 The area ratio of ferrite at the position of 1/4 of the plate thickness of the cross section parallel to the rolling direction and perpendicular to the surface was determined according to the above method. By the same method, the area ratio of ferrite was obtained at 10 points at intervals of 50 mm in the plate width direction, and the standard deviation of the area ratio was calculated.
[0100]
 The standard deviation of the surface roughness Ra measured at 10 positions at 50 mm intervals in the plate width direction was determined by the following procedure. Using a contact roughness meter (Mitutoyo surf test SJ-500), a roughness curve was obtained over a length of 5 mm in the plate width direction at each measurement position, and the arithmetic mean was obtained by the method described in JIS B0601: 2001. Roughness Ra was determined. The standard deviation of the surface roughness Ra was obtained by using the value of the arithmetic mean roughness Ra obtained at each measurement position thus obtained.
[0101]
 Tensile strength was determined by conducting a tensile test in accordance with JIS Z 2241 (2011) using JIS No. 5 test pieces collected from a high-strength steel plate so that the plate width direction is the longitudinal direction. TS (MPa) and butt elongation (total elongation) EL (%) were determined. The sampling was performed from 10 positions of the steel plate at intervals of 50 mm in the plate width direction. The average value of the tensile strengths of the 10 test pieces was regarded as the tensile strength TS of the steel sheet, and when TS ≧ 780 MPa was satisfied, it was judged as a high-strength hot-rolled steel sheet and passed.
 Further, the standard deviations of TS and EL at 10 positions at intervals of 50 mm in the plate width direction were obtained. A steel sheet having a TS standard deviation of 50 MPa or less and an EL standard deviation of 1% or less was determined to be a steel sheet having excellent material stability.
[0102]
 The drilling ratio was evaluated by a drilling test based on the test method described in the Japan Iron and Steel Federation standard JFS T 1001-1996.
[0103]
 The bending test was performed in accordance with JIS Z2248 (V block 90 ° bending test), and the bending radius (mm) was tested at a pitch of 0.5 mm.
 Further, R / t was measured at 10 positions at intervals of 50 mm in the plate width direction, and the standard deviation was obtained.
[0104]
[Table 4]

[0105]
[Table 5]

[0106]
 In Tables 4 and 5, values ​​outside the scope of the invention are underlined. As shown in the table, in the examples satisfying the conditions of the present invention, all of the tensile strength, elongation, hole widening property (stretch flange property), bendability, variation in tensile strength, and variation in elongation were excellent. On the other hand, in the comparative example in which at least one of the conditions of the present invention is not satisfied, at least one of tensile strength, elongation, hole widening property (stretch flange property), bendability, variation in tensile strength, and variation in elongation The characteristics were not sufficient.
[0107]
 Specifically, in Comparative Example 9 and Comparative Example 10, the standard deviation of the ferrite area ratio became large, and the TS standard deviation and the EL standard deviation were rejected. It is presumed that this is because hot rolling was performed under the condition that K'/ Si * was insufficient.
[0108]
 In Comparative Example 11, the proportion of retained austenite having an aspect ratio of 2.0 or more was insufficient, and the hole-spreading property was impaired. It is presumed that this is because the average cooling rate after finish rolling was insufficient.
[0109]
 In Comparative Example 12, the proportion of retained austenite having an aspect ratio of 2.0 or more was insufficient, and the hole-spreading property was impaired. It is presumed that this is because the take-up temperature after finish rolling was too high.
[0110]
 In Comparative Example 13, the ferrite area ratio was excessive, the area ratio of other structures was insufficient, and the tensile strength was insufficient. It is presumed that this is because the heating temperature in the annealing step was lower than the Ac1 point of the steel material A.
[0111]
 In Comparative Example 14, the proportion of retained austenite having an aspect ratio of 2.0 or more was insufficient, and the hole-spreading property was impaired. It is presumed that this is because the reduction rate under light reduction applied to the steel sheet before annealing of the steel sheet was excessive.
[0112]
 In Comparative Example 16, the amount of retained austenite was insufficient, and the total elongation and hole expandability were impaired. It is presumed that this is because the holding pattern in the annealing step was inappropriate, that is, the holding temperature was too low.
[0113]
 In Comparative Example 31 and Comparative Example 32, the amount of Si was insufficient. Therefore, in Comparative Example 31 and Comparative Example 32, the amount of retained austenite was insufficient, and the total elongation and the hole-expanding property were impaired.
Description of the sign
[0114]
1 High-strength steel plate (steel plate)
11 Surface (rolled surface)
12 Cross section
parallel to the rolling direction and perpendicular to the surface 121 Plate thickness 1/4 position of the cross section parallel to the rolling direction and perpendicular to the surface
13 Measurement surface of residual austenite
131 Residual Range of 1/8 to 3/8 thickness from the surface (rolled surface) on the measurement surface of austenite
RD Rolling Direction
TD Plate Thickness Direction (Tickness Direction)
WD Plate Width Direction (Wildth Direction)

WE CLAIMS

[Claim 1]As chemical components, in mass%,
  C: 0.030 to 0.280%,
  Si: 0.50 to 2.50%,
  Mn: 1.00 to 4.00%,
  sol. Al: 0.001 to 2.000%,
  P: 0.100% or less,
  S: 0.0200% or less,
  N: 0.01000% or less,
  O: 0.0100% or less,
  B: 0 to 0.010 %,
  Ti: 0 to 0.20%,
  Nb: 0 to 0.20%,
  V: 0 to 1.000%,
  Cr: 0 to 1.000%,
  Mo: 0 to 1.000%,
  Cu: 0 ~ 1.000%,
  Co: 0 to 1.000%,
  W: 0 to 1.000%,
  Ni: 0 to 1.000%,
  Ca: 0 to 0.0100%,
  Mg: 0 to 0.0100% ,
  REM: 0-0.0100%,
  Zr: 0-0.0100%, and
  balance: Fe and impurities
In terms
 of area ratio,
  ferrite: 20% to 70%,
  retained austenite: 5% to 40%,
  fresh martensite: 0% to 30%,
  total of tempered martensite and bainite: 20% to 75% and
  total of pearlite and cementite: 0% to 10%  , with an aspect ratio of 2.0 or more to the total number of retained austenite in the range of 1/8 to 3/8 thickness from
the surface. The
number ratio is 50% or more, and
 the area ratio of ferrite measured at 10 points every 50 mm along the plate width direction at the plate thickness 1/4 position of the cross section parallel to the rolling direction and perpendicular to the surface. A high-strength steel plate having a standard deviation of less than 10% and a
 tensile strength of 780 MPa or more .
[Claim 2]
 The high-strength steel sheet according to claim 1, wherein the standard deviation of the surface roughness Ra is 0.5 μm or less at 10 positions at intervals of 50 mm in the plate width direction.
[Claim 3]
 As the chemical components, in terms of mass%,
 B: 0.001% to 0.010%,
 Ti: 0.01 to 0.20%,
 Nb: 0.01 to 0.20%,
 V: 0.005% to 1.000%,
 Cr: 0.005% to 1.000%,
 Mo: 0.005% to 1.000%,
 Cu: 0.005% to 1.000%,
 Co: 0.005% to 1. 000%,
 W: 0.005% to 1.000%,
 Ni: 0.005% to 1.000%,
 Ca: 0.0003% to 0.0100%,
 Mg: 0.0003% to 0.0100% ,
 REM: 0.0003% to 0.0100%, and
 Zr: 0.0003% to 0.0100
 %
. High-strength steel plate.

Documents

Application Documents

# Name Date
1 202117046650-ABSTRACT [23-12-2024(online)].pdf 2024-12-23
1 202117046650-FORM 3 [09-09-2024(online)].pdf 2024-09-09
1 202117046650-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [13-10-2021(online)].pdf 2021-10-13
2 202117046650-STATEMENT OF UNDERTAKING (FORM 3) [13-10-2021(online)].pdf 2021-10-13
2 202117046650-FER.pdf 2024-06-26
2 202117046650-CLAIMS [23-12-2024(online)].pdf 2024-12-23
3 202117046650-COMPLETE SPECIFICATION [23-12-2024(online)].pdf 2024-12-23
3 202117046650-FORM 18 [15-06-2023(online)].pdf 2023-06-15
3 202117046650-PROOF OF RIGHT [13-10-2021(online)].pdf 2021-10-13
4 202117046650-DRAWING [23-12-2024(online)].pdf 2024-12-23
4 202117046650-FORM 3 [25-02-2022(online)].pdf 2022-02-25
4 202117046650-PRIORITY DOCUMENTS [13-10-2021(online)].pdf 2021-10-13
5 202117046650-Verified English translation [08-02-2022(online)].pdf 2022-02-08
5 202117046650-POWER OF AUTHORITY [13-10-2021(online)].pdf 2021-10-13
5 202117046650-FER_SER_REPLY [23-12-2024(online)].pdf 2024-12-23
6 202117046650.pdf 2021-10-23
6 202117046650-FORM-26 [23-12-2024(online)].pdf 2024-12-23
6 202117046650-FORM 1 [13-10-2021(online)].pdf 2021-10-13
7 202117046650-DRAWINGS [13-10-2021(online)].pdf 2021-10-13
7 202117046650-COMPLETE SPECIFICATION [13-10-2021(online)].pdf 2021-10-13
7 202117046650-OTHERS [23-12-2024(online)].pdf 2024-12-23
8 202117046650-DECLARATION OF INVENTORSHIP (FORM 5) [13-10-2021(online)].pdf 2021-10-13
8 202117046650-FORM 3 [09-09-2024(online)].pdf 2024-09-09
9 202117046650-COMPLETE SPECIFICATION [13-10-2021(online)].pdf 2021-10-13
9 202117046650-DRAWINGS [13-10-2021(online)].pdf 2021-10-13
9 202117046650-FER.pdf 2024-06-26
10 202117046650-FORM 1 [13-10-2021(online)].pdf 2021-10-13
10 202117046650-FORM 18 [15-06-2023(online)].pdf 2023-06-15
10 202117046650.pdf 2021-10-23
11 202117046650-FORM 3 [25-02-2022(online)].pdf 2022-02-25
11 202117046650-POWER OF AUTHORITY [13-10-2021(online)].pdf 2021-10-13
11 202117046650-Verified English translation [08-02-2022(online)].pdf 2022-02-08
12 202117046650-FORM 3 [25-02-2022(online)].pdf 2022-02-25
12 202117046650-PRIORITY DOCUMENTS [13-10-2021(online)].pdf 2021-10-13
12 202117046650-Verified English translation [08-02-2022(online)].pdf 2022-02-08
13 202117046650-FORM 18 [15-06-2023(online)].pdf 2023-06-15
13 202117046650-PROOF OF RIGHT [13-10-2021(online)].pdf 2021-10-13
13 202117046650.pdf 2021-10-23
14 202117046650-COMPLETE SPECIFICATION [13-10-2021(online)].pdf 2021-10-13
14 202117046650-FER.pdf 2024-06-26
14 202117046650-STATEMENT OF UNDERTAKING (FORM 3) [13-10-2021(online)].pdf 2021-10-13
15 202117046650-DECLARATION OF INVENTORSHIP (FORM 5) [13-10-2021(online)].pdf 2021-10-13
15 202117046650-FORM 3 [09-09-2024(online)].pdf 2024-09-09
15 202117046650-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [13-10-2021(online)].pdf 2021-10-13
16 202117046650-DRAWINGS [13-10-2021(online)].pdf 2021-10-13
16 202117046650-OTHERS [23-12-2024(online)].pdf 2024-12-23
17 202117046650-FORM 1 [13-10-2021(online)].pdf 2021-10-13
17 202117046650-FORM-26 [23-12-2024(online)].pdf 2024-12-23
18 202117046650-FER_SER_REPLY [23-12-2024(online)].pdf 2024-12-23
18 202117046650-POWER OF AUTHORITY [13-10-2021(online)].pdf 2021-10-13
19 202117046650-DRAWING [23-12-2024(online)].pdf 2024-12-23
19 202117046650-PRIORITY DOCUMENTS [13-10-2021(online)].pdf 2021-10-13
20 202117046650-PROOF OF RIGHT [13-10-2021(online)].pdf 2021-10-13
20 202117046650-COMPLETE SPECIFICATION [23-12-2024(online)].pdf 2024-12-23
21 202117046650-STATEMENT OF UNDERTAKING (FORM 3) [13-10-2021(online)].pdf 2021-10-13
21 202117046650-CLAIMS [23-12-2024(online)].pdf 2024-12-23
22 202117046650-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [13-10-2021(online)].pdf 2021-10-13
22 202117046650-ABSTRACT [23-12-2024(online)].pdf 2024-12-23
23 202117046650-PatentCertificate30-05-2025.pdf 2025-05-30
24 202117046650-IntimationOfGrant30-05-2025.pdf 2025-05-30

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