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Steel Sheet

Abstract: This invention pertains to a steel sheet that combines moldability and weldability. This steel sheet is characterized by, in the surface layer portion which is the region up until a depth of 30 µm in the thickness direction from the surface of the steel sheet, aluminum oxide particles being present at a density of 3000-6000 particles/mm2, the natural logarithm of the particle diameter of aluminum oxide particles measured in µm units having an average of -5.0 to -3.5, a standard deviation not exceeding 0.8, the number of aluminum oxide particles having a deviation from the average of the natural logarithm of the particle diameter being greater than double the standard deviation not exceeding 5% of the total number of aluminum oxide particles, and at a depth of 1/2 the thickness of the steel sheet, the density of aluminum oxide particles does not exceed 1000 particles/mm2.

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Patent Information

Application #
Filing Date
14 September 2021
Publication Number
41/2022
Publication Type
INA
Invention Field
METALLURGY
Status
Email
mahua.ray@remfry.com
Parent Application
Patent Number
Legal Status
Grant Date
2024-06-18
Renewal Date

Applicants

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

Inventors

1. SUZUKI, Yuya
c/o NIPPON STEEL CORPORATION, 6-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo 1008071

Specification

Invention Name : Steel Plate
Technical field
[0001]
 The present invention relates to steel sheets.
Background technology
[0002]
 BACKGROUND ART In recent years, from the viewpoint of improving the fuel efficiency of automobiles, which leads to environmental conservation, it has been demanded to increase the strength of steel sheets for automobiles, to make them thinner, and to reduce the weight of automobiles. In addition, steel sheets used for automobile parts are required to have excellent formability because they are formed into various shapes. Furthermore, since formed parts are welded in the assembly process of automobiles, good weldability is also important as a criterion for selecting steel sheets used for structural parts of automobiles.
[0003]
 By the way, in the welding of steel plates, a decrease in the strength of welded joints may pose a problem, as described in Patent Document 1 below, for example. If the toughness of the nugget formed during welding is low, it is believed that cracks occur and propagate within the nugget, resulting in a decrease in the strength of the welded joint.
prior art documents
patent literature
[0004]
Patent Document 1: Japanese Patent No. 6388099
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0005]
 The cracks in the nugget as described above occur and propagate in the surface layer of the steel sheet. Therefore, the weldability of the steel sheet is considered to be greatly affected by the condition of the surface layer. However, there is no prior art that improves the weldability of steel sheets by modifying the surface layer. Accordingly, an object of the present invention is to provide a steel sheet that achieves both formability and weldability.
Means to solve problems
[0006]
 The present inventors have studied how to suppress the decrease in welded joint strength caused by the occurrence and propagation of cracks in the nugget by modifying the surface layer of the steel sheet. As a result, the present inventors thought that by increasing the toughness of the nugget in the surface layer of the steel plate, it is possible to suppress the decrease in the strength of the welded joint and improve the weldability.
[0007]
 First, the present inventors produced a plurality of steel sheets in which a large number of Al oxide particles were distributed in the surface layer portion, and investigated the weldability of these steel sheets. As a result, all of these steel plates had improved weldability. Although the mechanism of this effect is not completely clear, it is thought as follows.
[0008]
 It is thought that the Al oxide particles distributed in the surface layer of the steel sheet suppress coarsening of austenite by becoming pinning particles during welding. When austenite coarsening is suppressed, the prior austenite grain size of martensite generated by cooling during welding becomes finer. It is considered that refinement of the prior austenite grain size of martensite improves the toughness of the nugget. As a result, it is thought that the occurrence and propagation of cracks in the nugget are suppressed and the weldability is improved.
[0009]
 However, it was found that, although weldability improved, formability deteriorated depending on the distribution state of Al oxide particles, and the present inventors continued more detailed investigations. As a result, the present inventors found that it is important to appropriately control the distribution of Al oxide particles in the surface layer of the steel sheet so as not to deteriorate the formability.
[0010]
 The gist of the present invention obtained as described above is as follows.
[0011]
 (1) A steel plate having a tensile strength of 780 MPa or more, and when a region from the surface of the steel plate to 30 μm in the plate thickness direction is defined as the surface layer portion, the surface layer portion on at least one side has Al with a grain size of 20 nm or more. The oxide particles exist at a number density of 3000 to 6000/mm 2 , and the natural logarithm of the particle size of the Al oxide particles measured in μm has an average of −5.0 to −3.5 and a standard deviation. is 0.8 or less, and the number of Al oxide particles whose deviation from the average of the natural logarithm of the particle size is greater than twice the standard deviation is the total number of Al oxide particles having a particle size of 20 nm or more. 5% or less, and the chemical composition at a position 1/4 of the plate thickness from the surface of the steel plate is, in mass%, C: 0.050 to 0.800%, Si: 0.01 to 1.20%, Mn: 0.01-8.00%, P: 0.100% or less, S: 0.050% or less, Al: 0-3.000%, N: 0.010% or less, O: 0-0. 020%, Cr: 0-3.00%, Mo: 0-1.00%, B: 0-0.0100%, Ti: 0-0.200%, Nb: 0-0.200%, V: 0 to 0.20%, Cu: 0 to 1.000%, Ni: 0 to 1.000%, the balance: Fe and impurities, Al oxide particles at 1/2 the thickness of the steel plate A steel plate, wherein the number density of is 1000/mm 2 or less.
[0012]
 (2) The chemical composition is, in mass%, Cr: 0.01 to 3.00%, Mo: 0.01 to 1.00%, B: 0.001 to 0.0100%, Ti: 0.010 ~0.200%, Nb: 0.010-0.200%, V: 0.01-0.20%, Cu: 0.010-1.000%, and Ni: 0.010-1.000% The steel sheet according to (1), comprising at least one selected from the group consisting of
[0013]
 (3) The steel sheet according to (1) or (2) above, wherein the metal structure at a position 1/4 of the thickness from the surface of the steel sheet contains 10% or more of retained austenite in area ratio.
[0014]
 (4) The steel sheet according to any one of (1) to (3), further including a hot-dip galvanized layer, an alloyed hot-dip galvanized layer, or an electro-galvanized layer on the surface of the surface layer portion.
Effect of the invention
[0015]
 ADVANTAGE OF THE INVENTION According to this invention, the steel plate which can make formability and weldability compatible can be provided. Such a steel sheet of the present invention is suitable as a material for automobile parts and the like.
Brief description of the drawing
[0016]
1] Fig. 1 is a schematic diagram showing an example of a method of adding iron oxide to the surface layer of molten steel in the continuous casting step of the steel sheet manufacturing method of the present invention. [Fig.
MODE FOR CARRYING OUT THE INVENTION
[0017]
 Embodiments of the present invention will be described below. In addition, the embodiment illustrated below is for facilitating understanding of the present invention, and is not for limiting and interpreting the present invention. The present invention can be modified and improved from the following embodiments without departing from its spirit. It should be noted that "~" in the numerical range expression means that the number on the left side is included as the lower limit and the number on the right side is included as the upper limit.
[0018]
 The steel sheet according to the present embodiment has a tensile strength of 780 MPa or more, preferably 900 MPa or more. In the steel sheet according to the present embodiment, a region up to 30 μm in the plate thickness direction from the surface of the steel plate is defined as the surface layer portion, and a region inside the plate thickness direction from the surface layer portion is defined as the steel plate central portion. The surface layer portion of the steel sheet according to this embodiment satisfies the following conditions.
[0019]
 Al oxide particles are present in the surface layer on at least one side of the steel sheet. The surface layer portion may be formed only on one side of the steel sheet, or may be formed on both sides of the steel sheet. In this embodiment, the Al oxide particles have a number density of 3000 to 6000/mm 2 . The particle size of the Al oxide particles in this embodiment follows the particle size distribution below. That is, the natural logarithm of the particle size of Al oxide particles measured in units of μm has an average of −5.0 to −3.5 or less and a standard deviation of 0.8 or less. In addition, the number of Al oxide particles whose grain size deviates from the mean of the natural logarithm by more than twice the standard deviation is 5% or less of the total number of Al oxide particles to be measured in the surface layer portion. By satisfying the above conditions for Al oxides, it is possible to achieve both formability and weldability for a high-strength steel sheet having a tensile strength of 780 MPa or more.
[0020]
 The average natural logarithm of the particle size of Al oxide particles measured in μm is −3.5 or less. This suppresses the occurrence of cracks originating from the coarse Al oxide particles during the forming of the steel sheet, and suppresses the deterioration of the formability of the steel sheet. From that point of view, the average is more preferably -3.6 or less, and even more preferably -3.8 or less. In the present invention, the formability is obtained by taking a Japanese Industrial Standards JIS No. 5 test piece from a steel plate perpendicular to the rolling direction and performing a tensile test on the test piece in accordance with JIS Z 2241 (2011). pointing to elongation. On the other hand, the weldability of the steel sheet is improved by setting the average natural logarithm of the particle size of the Al oxide particles measured in units of μm to −5.0 or more. From that point of view, the average is preferably −4.9 or more, more preferably −4.7 or more.
[0021]
 Moreover, the standard deviation of the natural logarithm of the particle size of the Al oxide particles measured in units of μm is 0.8 or less. This suppresses the occurrence of cracks originating from the coarse Al oxide particles during the forming of the steel sheet, and suppresses the deterioration of the formability of the steel sheet. The lower limit of the standard deviation is ideally zero. It is technically difficult to make the lower limit of the standard deviation less than 0.2. Therefore, the lower limit of the standard deviation may be set to 0.2.
[0022]
 Furthermore, in the above particle size distribution, the proportion of Al oxide particles exceeding twice the standard deviation of the mean of the natural logarithm of the particle size is limited to 5% or less of the total Al oxide particles. By controlling the particle size of the Al oxide particles in this way, cracks originating from coarse Al oxide particles during steel sheet forming are suppressed, and deterioration of the formability of the steel sheet is suppressed. be. The lower limit of the above ratio is ideally zero. Since it is technically difficult to make the above ratio less than 1%, the lower limit may be 1%.
[0023]
 The number density of many Al oxide particles present in the surface layer on at least one side of the steel sheet is 3000 to 6000/mm 2 . By setting the number density of Al oxide particles present in the surface layer of the steel sheet to 3000/mm 2 or more, the toughness of the nugget can be improved, the decrease in weld joint strength can be suppressed, and the weldability can be improved. On the other hand, by setting the number density of Al oxide particles present in the surface layer of the steel sheet to 6000/mm 2 or less, the deterioration of formability of the steel sheet can be suppressed. From this point of view, the number density of Al oxide particles is more preferably 5500/mm 2 or less, and even more preferably 5000/mm 2 or less.
[0024]
 Al oxide particles may be present over a range of up to 30 μm from the surface. When many Al oxide particles are present on both sides of the steel sheet, the respective surface layer portions may be formed under the same conditions, or the respective surface layer portions may be formed under mutually different conditions. In this case, if one surface layer satisfies the above conditions, the other surface layer does not have to satisfy the above conditions, but both surface layer portions preferably satisfy the above conditions. If the surface layer portion that satisfies the above conditions is used as the joining surface, the toughness of the nugget can be enhanced and the strength of the welded joint can be ensured.
[0025]
 In the present invention, the "number density of Al oxide particles in the surface layer" and the "particle size distribution of Al oxide particles in the surface layer" are determined as follows.
[0026]
 The number and grain size of Al oxide particles can be identified by observing a cross section parallel to the rolling direction and thickness direction of the steel sheet at a magnification of 10000 times. Specifically, first, a section of the cut steel sheet is mechanically polished to a mirror finish, and then a nital reagent is used to expose the steel structure. After that, a 0.04 mm area (area included in the surface layer ) centered at a position 15 μm in the plate thickness direction from the surface of the steel sheet (a position half the thickness of the surface layer) was scanned with a scanning electron microscope. (SEM: scanning electron microscope) is used to observe the steel structure. The value obtained by converting the number of Al oxide particles observed and counted in this manner into the number per 1 mm 2 is defined as the "number density of Al oxide particles in the surface layer portion". In addition, the particle size of the Al oxide particles obtained by measuring in the same region (equivalent diameter of the circumscribed circle) and the frequency at which each particle size value is measured are referred to as the "particle size distribution of the Al oxide particles in the surface layer. ”. Here, the Al oxide particles included in the number of Al oxide particles have a particle size of 20 nm or more.
[0027]
 Although the mechanism of this effect is not completely clear, it is thought as follows. If the particle size of the Al oxide particles present in the surface layer portion does not conform to the above particle size distribution, it is considered that many coarse Al oxide particles tend to be present in the surface layer portion. These coarse Al oxide particles cause concentration of strain and stress during forming of the steel sheet, and the generation of voids may cause cracks. On the other hand, since the particle diameters of the large number of Al oxide particles distributed in the surface layer follow the particle diameter distribution, the occurrence of cracks due to coarse Al oxide particles is suppressed while promoting the coarsening of austenite as described above. obtain. Therefore, it is considered that the weldability could be improved while suppressing the deterioration of the formability of the steel sheet.
[0028]
 It was not confirmed that the weldability of the steel sheet was significantly affected by the number density and particle size of the Al oxide particles in portions other than the surface layer of the steel sheet. For this reason, even when DP (Dual Phase) steel or TRIP (Transformation Induced Plasticity) steel, which has excellent ductility and is conventionally considered to be disadvantageous in weldability, is used in the central portion of the steel plate, the surface layer portion can be used as described above. One of the excellent points of the present invention is that a steel plate having excellent weldability can be obtained by forming as described above.
[0029]
 However, from the viewpoint of suppressing the deterioration of the formability of the steel sheet, it is preferable that the number density of the Al oxide particles existing in the center of the steel sheet is small. Specifically, the number density of Al oxide particles is set to 1000 particles/mm 2 or less at the center of the steel sheet in the thickness direction (the position at 1/2 of the thickness). Within this region, the steel structure of a region of 0.04 mm 2 centered at the position of 1/2 of the plate thickness is observed at a magnification of 10,000 in the same manner as described above. The value obtained by converting the number of Al oxide particles observed and counted in this manner into the number per 1 mm 2 is defined as the number density of Al oxide particles at the center of the steel sheet.
[0030]
 Further, in order to further improve the formability of the steel sheet of the present embodiment, it is preferable that the center portion of the steel sheet contains retained austenite at an area ratio of 10% or more. Specifically, it is preferable that the metal structure at a position of 1/4 of the plate thickness from the surface of the steel plate contains retained austenite at an area ratio of 10% or more. Since ductility is improved by transformation-induced plasticity of retained austenite, the total elongation of the steel sheet can be increased to 15% or more by setting the area ratio of retained austenite to 10% or more. By using the effect of this retained austenite, a total elongation of 15% or more can be secured even if soft ferrite is not included. Therefore, the strength of the center portion of the steel sheet can be increased, and both the strength increase of the steel sheet and the improvement of formability can be achieved.
[0031]
 In the present invention, the volume ratio of retained austenite determined as follows is regarded as the area ratio of retained austenite in the center of the steel sheet. The volume fraction of retained austenite can be determined by an X-ray diffraction method. First, a sample having a plate thickness cross-section parallel to the rolling direction of the steel plate is taken. Of this sample, the surface of the steel plate to the position of 1/4 of the plate thickness is removed by mechanical polishing and chemical polishing, and the surface of the position of 1/4 of the plate thickness is exposed from the surface of the steel plate. Then, the surface exposed in this way is irradiated with MoKα rays, and the diffraction of the (200) plane and (211) plane of the bcc phase and the (200) plane, (220) plane and (311) plane of the fcc phase Calculate the integrated intensity ratio of the peak. The volume fraction of retained austenite can be calculated from the integrated intensity ratio of the diffraction peaks. As this calculation method, a general 5-peak method can be used.
[0032]
 Next, the chemical composition of the steel sheet of the present invention will be described. In the steel sheet of the present invention, it is preferable that the chemical composition of the central portion of the steel sheet satisfies the following conditions. The chemical composition at the center of the steel sheet means the chemical composition measured at a position 1/4 of the thickness from the surface of the steel sheet. "%" regarding the content of an element means "% by mass" unless otherwise specified.
[0033]
 "C: 0.050 to 0.800%"
 C is an element that increases the strength of the steel sheet. In order to obtain the effect of sufficiently increasing the strength of the steel sheet with C, the C content is made 0.050% or more. Further, when the C content is 0.800% or less, a decrease in toughness of the steel sheet can be suppressed. From that point of view, the C content is preferably 0.600% or less, more preferably 0.500% or less.
[0034]
 "Si: 0.01 to 1.20%"
 Si is an element that stabilizes ferrite. That is, since Si increases the Ac3 transformation point, it is possible to form a large amount of ferrite in a wide annealing temperature range, and is added from the viewpoint of improving the structure controllability of steel. In order to obtain such effects of Si, the Si content should be 0.01% or more. In addition, Si is an element that suppresses the coarsening of iron-based carbides and increases the strength and formability of the steel sheet. Moreover, Si is added as a solid-solution strengthening element in order to contribute to increasing the strength of the steel sheet. From these points of view, the Si content is preferably 0.2% or more, more preferably 0.5% or more. From the viewpoint of suppressing deterioration of formability due to brittleness of the steel sheet, the Si content is set to 1.20% or less. The Si content is preferably 1.00% or less.
[0035]
 "Mn: 0.01 to 8.00%"
 Mn is an element that enhances the hardenability of steel. In order to obtain such effects by Mn, the content of Mn is set to 0.01% or more. The content of Mn is set to 8.00% or less from the viewpoint of preventing the segregation of Mn and the hardness difference from becoming too large. The Mn content is preferably 5.00% or less, more preferably 4.00%, and even more preferably 3.00% or less.
[0036]
 "P: 0.100% or less"
 P is an element that may segregate and embrittle the weld zone. Therefore, it is preferable that the P content is small. Specifically, the P content is set to 0.100% or less. The lower limit of the P content is zero. Since it is economically disadvantageous to make the P content less than 0.001%, the lower limit may be 0.001%.
[0037]
 "S: 0.050% or less"
 S is an element that may adversely affect the weldability of steel sheets and the manufacturability during casting and hot rolling. Therefore, it is preferable that the content of S is small. Specifically, the content of S is set to 0.050% or less. The lower limit of the S content is zero. Since it is economically disadvantageous to make the S content less than 0.001%, the lower limit may be 0.001%.
[0038]
 "Al: 0 to 3.000%"
 Al is an element that acts as a deoxidizing agent and is added in the deoxidizing step as necessary. When using Al as a deoxidizing agent, the steel sheet may contain 0.050% or less of Al. As will be described later, when different steel sheets are laminated and joined to produce the hot-rolled steel sheet of the present invention, if a predetermined Al oxide is contained in the surface layer portion, 1/4 of the thickness from the surface of the steel sheet The position need not contain Al, and the Al amount may be zero. In addition, as will be described later, when oxygen is supplied to the surface layer of the slab to form Al oxide particles on the surface layer of the steel sheet, it is necessary to supply Al from the slab, so the slab contains 0.010% Al. The content is preferably 0.100% or more, more preferably 0.100% or more, and further preferably 0.300% or more, or 0.800% or more. In this case, the Al content at the 1/4 thickness position from the surface of the steel sheet may be 0.500% or more, or 0.800% or more, depending on the amount of Al contained in the slab. On the other hand, from the viewpoint of suppressing slab cracking during continuous casting, the Al content is preferably 3.000% or less.
[0039]
 "N: 0.010% or less"
 N may form coarse nitrides and deteriorate the bendability of the steel sheet. Also, N may cause blowholes during welding. Therefore, it is preferable that the content of N is small. Specifically, the content of N is set to 0.010% or less. The lower limit of the N content is zero. Since it is economically disadvantageous to make the N content less than 0.001%, the lower limit may be 0.001%.
[0040]
 "O: 0 to 0.020%"
 O is an element necessary for forming an Al oxide on the surface layer. However, if an Al oxide is formed on the surface layer, O may not exist at a position 1/4 of the plate thickness from the surface. Therefore, the lower limit of the O content at the position of 1/4 of the plate thickness from the surface is 0. However, the lower limit may be 0.001% in order to efficiently form an Al oxide on the surface layer. The upper limit is made 0.020% because the elongation decreases when the amount of O at the position of 1/4 of the plate thickness from the surface increases.
[0041]
 The rest of the chemical composition in the center of the steel sheet is Fe and impurities. However, the following elements may be contained instead of part of Fe.
[0042]
 "Cr: 0 to 3.00%, Mo: 0 to 1.00%, B: 0 to 0.0100%"
 Cr, Mo and B each improve the hardenability of the steel and contribute to the improvement of the strength of the steel plate. It is an element that The effect of containing these elements can be obtained even if the content of these elements is small. The content of these elements may be 0%, but in order to sufficiently obtain the above effects, the Cr content is 0.01% or more, the Mo content is 0.01% or more, and the B content is It is preferably 0.0001% or more. On the other hand, from the viewpoint of suppressing deterioration of the pickling property, weldability, hot workability, etc. of the steel sheet, the Cr content is 3.00% or less, the Mo content is 1.00% or less, and the B content is is 0.0100% or less.
[0043]
 "Ti: 0 to 0.200%, Nb: 0 to 0.200%, V: 0 to 0.20%"
 Ti, Nb and V are elements that contribute to improvement in strength of the steel sheet. These elements contribute to increasing the strength of the steel sheet by strengthening precipitates, strengthening fine grains by suppressing the growth of ferrite grains, and strengthening dislocations by suppressing recrystallization. The effect of containing these elements can be obtained even if the content of these elements is small. The content of these elements may be 0%, but in order to sufficiently obtain the above effects, the content of each of Ti and Nb should be 0.010% or more, and the content of V should be 0.01% or more. is preferred. However, from the viewpoint of suppressing the deterioration of the formability of the steel sheet due to an increase in the precipitation of carbonitrides, the content of each of Ti and Nb is 0.200% or less, and the content of V is 0.20%. Below.
[0044]
 "Cu: 0 to 1.000%, Ni: 0 to 1.000%"
 Cu and Ni are elements that contribute to improvement in the strength of the steel sheet. The effect of containing these elements can be obtained even if the content of these elements is small. Although the content of these elements may be 0%, the content of Cu and Ni is preferably 0.010% or more in order to sufficiently obtain the above effects. On the other hand, from the viewpoint of suppressing deterioration of pickling properties, weldability, hot workability, etc. of the steel sheet, the contents of Cu and Ni are set to 1.000% or less, respectively.
[0045]
 Furthermore, the following elements may be intentionally or unavoidably contained in the center of the steel sheet in place of part of Fe within the range where the effects of the present invention can be obtained. That is, the steel sheet of the present embodiment has W: 0 to 0.1%, Ta: 0 to 0.1%, Sn: 0 to 0.05%, Sb: 0 to 0.05%, As: 0 to 0 .05%, Mg: 0-0.05%, Ca: 0-0.05%, Zr: 0-0.05%, and Y: 0-0.05%, La: 0-0.05%, And REM (Rare-Earth Metal) such as Ce: 0 to 0.05% may be contained in the center of the steel sheet.
[0046]
 The steel sheet of the present invention may further include a hot-dip galvanized layer, an alloyed hot-dip galvanized layer, or an electrogalvanized layer on the surface of the surface layer portion. Even when the plating layer is formed in this way, the steel sheet of the present invention can achieve both formability and weldability by modifying the surface layer portion as described above.
[0047]
 Next, an example of a manufacturing method for obtaining the steel sheet of the present invention will be described.
[0048]
 In the present invention, the particle size of many Al oxide particles contained in the surface layer portion is controlled so as to conform to the above particle size distribution. A method for manufacturing a steel sheet according to the present invention for controlling the number density and particle size of Al oxide particles will be described below. The steel sheet of the present invention includes hot-rolled steel sheet, cold-rolled steel sheet, plated steel sheet and the like.
[0049]
 [Hot-rolled steel sheet]
[0050]
 In the present embodiment, the method for controlling Al oxides is not particularly limited. A steel sheet corresponding to the surface layer portion in which particles are distributed is separately manufactured, and these steel sheets are laminated and joined to form a multi-layer steel sheet. A method of leaving scale on the steel plate surface can be exemplified.
[0051]
 A method for controlling the distribution of Al oxide particles in the surface layer by wire addition will be described below.
[0052]
 In the process of flowing the molten steel that satisfies the chemical composition of the center of the steel plate from the tundish to the continuous casting machine, wire-shaped iron oxide is added to a portion corresponding to the surface layer of the steel plate to obtain a slab. FIG. 1 is a schematic diagram showing a method of adding wire-shaped iron oxide to the surface layer of molten steel in the continuous casting process of the steel sheet manufacturing method of the present invention. In this way, iron oxide is added to the surface layer of the molten steel, and oxygen contained in the iron oxide combines with Al to form Al oxide particles.
[0053]
 When wire-shaped iron oxide is added to molten steel, wire-shaped iron oxide having a diameter of 1 mm or more and 50 mm or less is used. By setting the diameter of the wire (wire diameter) to 1 mm or more, the average of the particle size distribution according to the particle size of the Al oxide particles can be -5.0 or more. On the other hand, by setting the wire diameter to 50 mm or less, the average of the particle size distribution can be -3.5 or less. Further, by setting the wire diameter to 50 mm or less, the standard deviation of the particle size distribution can be set to 0.8 or less.
[0054]
 In addition, the wire-shaped iron oxide is such that the wire center passes through a position that is at least the wire diameter (mm unit) from the surface of the molten steel, and the wire diameter (mm unit) + 30 mm or less, and the distance between the wire centers is the wire diameter ( mm unit) or more and wire diameter (mm unit) + 30 mm or less. By controlling the positions of the wire centers and the intervals between the wires in this way, the distribution of Al oxides in the surface layer of the steel sheet and the number density of Al oxides in the center of the steel sheet can be appropriately adjusted.
[0055]
 The wire-shaped iron oxide is added to the molten steel so that the difference between the wire feed rate and the flow rate of the molten steel is −500 mm/min or more and 500 mm/min or less. By adding iron oxide to molten steel in this manner, the number density of Al oxide particles in the surface layer can be controlled to 3000/mm 2 or more and 6000/mm 2 or less. The number density of Al oxide particles tends to decrease as the wire feed speed increases, and the number density of Al oxide particles tends to increase as the wire feed speed decreases.
[0056]
 As described above, after forming a slab having a layer that will be the central portion of the steel sheet and a layer that will be the surface layer portion in which Al oxide particles are distributed, Heat the slab at the heating temperature. By setting the heating temperature of the slab to 1100° C. or higher, the anisotropy of crystal orientation caused by casting can be suppressed. On the other hand, by setting the heating temperature of the slab to 1350° C. or less, it is possible to suppress a significant increase in the manufacturing cost.
[0057]
 After heating the slab as described above, the slab is subjected to hot rolling. This hot rolling process includes a rough rolling process and a finish rolling process at a finishing temperature of 800° C. or more and 980° C. or less. By setting the finish temperature of hot rolling to 800° C. or higher, it is possible to suppress an increase in the rolling reaction force and to stably obtain a desired plate thickness. On the other hand, by setting the finish temperature of hot rolling to 980° C. or less, hot rolling can be completed without using a separate heating device in the process from the end of heating of the slab to the completion of hot rolling, and the production of steel sheet. A significant increase in cost can be suppressed.
[0058]
 After that, the hot-rolled steel sheet is cooled to a temperature of 550° C. or more and 750° C. or less at an average cooling rate of 2.5° C./s or more. This cooling step is a step necessary to convert most of the steel sheet into a low-temperature transformation structure and increase the strength of the steel sheet. By setting the average cooling rate to 2.5° C./s or more, ferrite transformation and pearlite transformation can be suppressed, and a decrease in the strength of the steel sheet can be suppressed. The average cooling rate is preferably 5°C/s or higher, more preferably 10°C/s or higher. However, at temperatures higher than 750° C., ferrite transformation and pearlite transformation are less likely to occur, so the average cooling rate is not limited. At temperatures lower than 550° C., the average cooling rate is not limited because the steel transforms into a low-temperature transformed structure.
[0059]
 Next, the steel sheet cooled in the cooling step is wound up. In this winding step, the winding temperature is set to 550° C. or lower. By setting the coiling temperature to 550° C. or lower, ferrite transformation and pearlite transformation in the surface layer of the steel sheet are suppressed. The winding temperature is preferably 500° C. or lower, more preferably 300° C. or lower. In this way, the hot-rolled steel sheet of the present invention can be obtained.
[0060]
 In order to further improve the formability of the steel sheet by increasing the area ratio of the retained austenite in the center of the steel sheet to 10% or more, it is preferable to include the following process instead of the process after the hot rolling. That is, the hot-rolled steel sheet is held at a temperature of 700° C. or less and 500° C. or more for 3 seconds or more in the cooling process, and then coiled at a temperature of martensite transformation start temperature Ms or more and bainite transformation start temperature Bs or less. is preferred. Here, the bainite transformation start temperature Bs and the martensite transformation start temperature Ms are calculated by the following equations.
[0061]
 Bs (°C) = 820-290C/(1-Sf)-37Si-90Mn-65Cr-50Ni+70Al
 Ms (°C)=541-474C/(1-Sf)-15Si-35Mn-17Cr-17Ni+19Al
 where C, Si , Mn, Cr, Ni and Al are the contents [mass %] of each element contained in the slab, and Sf is the area ratio of ferrite in the center of the steel sheet.
[0062]
 In addition, it is difficult to determine the area ratio of ferrite in the steel sheet during manufacture. For this reason, in the present invention, a steel sheet that has undergone the same temperature history as in the actual steel sheet manufacturing process is prepared in advance, the area ratio of ferrite in the center of the steel sheet is obtained, and the area ratio of ferrite is calculated from the above Bs and Used for calculation of Ms. The area ratio of ferrite can be obtained as follows. First, a sample having a plate thickness cross-section parallel to the rolling direction of the steel plate is taken, and the cross-section is used as an observation surface. A region of 100 μm×100 μm centered at a position of 1/4 of the plate thickness from the surface of the steel plate is defined as an observation region. An electron channeling contrast image obtained by observing this observation area with a scanning electron microscope at a magnification of 3000 is an image that displays the crystal orientation difference of crystal grains as a difference in contrast. In this electron channeling contrast image, the uniform contrast portion is ferrite. Then, the area ratio of ferrite identified in this way is calculated by the point counting method (based on ASTM E562).
[0063]
 [Cold-rolled steel sheet]
[0064]
 Next, an example of a method for manufacturing a cold-rolled steel sheet among the steel sheets included in the present invention will be described.
[0065]
 First, after obtaining a slab in the same manner as in the production example of the hot-rolled steel sheet, the slab is heated and hot rolled in the same manner as in the production example of the hot-rolled steel sheet. After that, the hot-rolled steel sheet is cooled and wound up in the same manner as in the manufacturing example of the hot-rolled steel sheet. However, in the winding process, the winding temperature is set at 20°C or higher and 700°C or lower.
[0066]
 Next, the hot-rolled steel sheet wound as described above is unwound and pickled. This pickling step is for removing oxides (scales) on the surface of the hot-rolled steel sheet, and may be performed once or in multiple steps.
[0067]
 Next, cold rolling is performed. In this cold rolling step, the total rolling reduction is preferably 85% or less. By setting the total rolling reduction to 85% or less, a decrease in ductility at the center of the steel sheet is suppressed, and breakage of the center of the steel sheet during cold rolling is suppressed. On the other hand, in order to sufficiently promote recrystallization in the subsequent annealing step, the total rolling reduction in the cold rolling step is preferably 20% or more, more preferably 30% or more. Before cold rolling, the steel sheet may be annealed at a temperature of 700° C. or lower for the purpose of reducing the cold rolling load.
[0068]
 Annealing is performed after the cold rolling process. In this annealing step, it is important to make most of the structure of the steel sheet into a low temperature transformation structure and suppress ferrite transformation and pearlite transformation in order to increase the strength of the steel sheet. In the annealing step, first, the steel plate is held at a temperature of Ac3 point at the center of the steel sheet -100° C. or more and 900° C. or less for 5 seconds or more. The reason why the heating temperature is set to Ac3 point −100° C. or higher at the center of the steel sheet is that the center of the steel sheet is heated to a two-phase region of ferrite and austenite or a single-phase region of austenite, and a transformation structure is obtained by subsequent heat treatment, This is for obtaining a steel sheet having a desired strength. On the other hand, by setting the heating temperature in the annealing step to 900° C. or less, it is possible to suppress the coarsening of the prior austenite grain size in the central portion of the steel sheet, and suppress the deterioration of the toughness of the steel sheet.
[0069]
 The Ac3 point is obtained by the following formula.
 Ac3(°C)=910-203√C+44.7Si-30Mn+700P-20Cu-15.2Ni-11Cr+31.5Mo+400Ti+104V+120Al
 where C, Si, Mn, P, Cu, Ni, Cr, Mo, Ti, V and Al are slabs is the content [% by mass] of each element contained in.
[0070]
 After the annealing step, the annealed steel sheet is cooled to a temperature of 550° C. or more and 750° C. or less at an average cooling rate of 2.5° C./s or more to obtain the cold-rolled steel sheet of the present invention. This cooling step is a step necessary for increasing the strength of the steel sheet. By setting the average cooling rate to 2.5° C./s or more, ferrite transformation and pearlite transformation can be suppressed, and a decrease in the strength of the steel sheet can be suppressed. The average cooling rate is preferably 5°C/s or higher, more preferably 10°C/s or higher. However, at temperatures higher than 750° C., ferrite transformation and pearlite transformation are less likely to occur, so the average cooling rate is not limited. At temperatures lower than 550° C., the average cooling rate is not limited because the steel transforms into a low-temperature transformed structure. At a temperature of 550° C. or less, the steel sheet may be cooled to room temperature at a constant cooling rate, and by holding the steel sheet at a temperature of about 200° C. or more and 550° C. or less, bainite transformation proceeds and martensite is tempered. You can However, if the steel sheet is held at 300° C. or higher and 550° C. or lower for a long period of time, the strength of the steel sheet may decrease.
[0071]
 In order to further improve the formability of the steel sheet by making the area ratio of the retained austenite in the center of the steel sheet 10% or more, instead of the annealing process after cold rolling described above, the following heating and cooling It is preferable to implement
[0072]
 First, the steel plate is heated to 700° C. or higher and 900° C. or lower and held for 5 seconds or more. The reason why the heating temperature is set to 700° C. or higher is to sufficiently promote recrystallization and reduce the non-recrystallized fraction. Further, by setting the heating temperature to 900° C. or less, coarsening of the grain size of the prior austenite in the central portion of the steel sheet and deterioration of the toughness are suppressed. Further, by setting the holding time to 5 seconds or more, the austenite transformation can be advanced and the decrease in the strength of the steel sheet can be suppressed. From this point of view, the retention time is preferably 10 seconds or longer, more preferably 20 seconds or longer.
[0073]
 The steel plate heated and held is cooled so that the center of the steel plate satisfies an average cooling rate of 10° C./s or more to a cooling stop temperature of Ms−100° C. or more and less than Bs. In this cooling, the average cooling rate in the temperature range of 750°C to 550°C is 2.5°C/s or more.
[0074]
 Further, in order to obtain a desired ferrite area ratio in this cooling process, the following pre-cooling process may be performed.
[0075]
 Optionally, pre-cooling the steel plate from the temperature to a pre-cooling stop temperature of the Bs point or more at the center of the steel plate and less than Ac3 point -40°C for 5 seconds or more and less than 400 seconds. Such a preliminary cooling step may be performed as necessary, and subsequent cooling steps may be performed without the preliminary cooling step.
[0076]
 After cooling, the temperature is controlled so that the center of the steel plate stays in the temperature range of 300 ° C to 500 ° C for 30 seconds to 600 seconds so that the area ratio of retained austenite in the center of the steel plate is 10% or more. . During this dwell, heating and cooling may optionally occur multiple times as required. This residence time is important for the stabilization of retained austenite. The methods for obtaining Ac3, Bs and Ms are as described above.
[0077]
 The above description is intended to be a mere illustration of the manufacturing method for obtaining the steel sheet of the present invention. As described above, the steel sheet manufacturing method of the present invention is not limited to the method of controlling the distribution of Al oxide particles in the surface layer portion by adding wires.
[0078]
 [Plated steel sheet]
[0079]
 Next, an example of a method for manufacturing a plated steel sheet included in the present invention will be described.
[0080]
 A hot-dip galvanized steel sheet is obtained by hot-dip galvanizing the surface of the cold-rolled steel sheet manufactured as described above. When hot-dip galvanization is applied, the plating bath temperature may be the conditions that have been conventionally applied. That is, the plating bath temperature is, for example, 440° C. or higher and 550° C. or lower.
[0081]
 Further, a hot-dip galvannealed steel sheet can be obtained by subjecting the hot-dip galvanized steel sheet to a heat-alloying treatment as described above. The heating temperature for alloying in the heat alloying treatment may be the conditions that have been conventionally applied. That is, the heating temperature for alloying is, for example, 400° C. or higher and 600° C. or lower. The heating method for alloying is not particularly limited, and a heating method suitable for conventional hot-dip plating equipment, such as direct heating by combustion gas, induction heating, or direct electric heating, can be used. After the alloying treatment, the steel sheet is cooled to 200° C. or less and subjected to temper rolling as necessary.
[0082]
 Moreover, the following examples are mentioned as a method of manufacturing an electrogalvanized steel sheet. For example, alkali degreasing, washing with water, pickling, and washing with water are performed in order as pretreatments for plating on the above cold-rolled steel sheet. After that, the pretreated steel sheet is coated with, for example, a liquid circulation type electroplating apparatus, using a plating bath consisting of zinc sulfate, sodium sulfate, and sulfuric acid, and applying a current density of about 100 A/dm 2 to a predetermined plating thickness. Electrolytically treat until
Example
[0083]
 In the process of manufacturing a continuously cast slab with a thickness of 250 mm having the chemical composition shown in Table 1, wire-shaped iron oxide is added under the conditions shown in Tables 2-1 to 2-3, and Al oxide is distributed in the surface layer. I got a slab that did. Tables 4-1 to 4-3 show whether the wire-shaped iron oxide was added to the surface layer on one side or the surface layer on both sides as the "position of the surface layer". This slab was subjected to hot rolling under the conditions of heating temperature, finishing temperature and coiling temperature shown in Tables 2-1 to 2-3 to obtain hot rolled steel sheets. For steel sheets to be cold-rolled steel sheets, after obtaining hot-rolled steel sheets as described above, cold rolling is performed with a total of pickling and rolling reduction of 50%, and under the conditions shown in Tables 2-1 to 2-3. Annealed. Further, some of the steel sheets were plated by a conventional method to obtain plated steel sheets as shown in Tables 2-1 to 2-3.
[0084]
 Further, some of the steel sheets were annealed as shown in Tables 3-1 to 3-3 in order to increase the area ratio of retained austenite in the central portion of the sheet thickness to 10% or more.
[0085]
 Evaluation results of the obtained steel sheets are shown in Tables 4-1 to 5-3. Details of the “number density”, “average”, “standard deviation”, “percentage deviation from the average” of Al oxides in the surface layer shown in Tables 5-1 to 5-3, and “area ratio of retained austenite” is as described above. In addition, Tables 4-1 to 4-3 show the chemical compositions of the obtained steel sheets at positions 1/4 of the thickness from the surface. Furthermore, the obtained steel sheets were subjected to a tensile test and a welding test as described below.
[0086]
 Tensile strength (MPa) and total elongation (%) were measured by preparing a JIS No. 5 test piece with the long axis perpendicular to the rolling direction according to JIS Z 2241 (2011) and performing a tensile test. be. In this example, a sample with a tensile strength of 780 MPa or more and a value of (tensile strength×total elongation) of 10000 MPa % or more was regarded as acceptable.
[0087]
 Welding tests were conducted as follows. A test piece described in JIS Z 3137 (1999) was taken from the steel plate, and another steel plate was welded to the test piece using a servomotor pressurized single-phase AC spot welder (power supply frequency 50 Hz). After that, the cross tension force was measured according to JIS Z 3137 (1999). In this example, the case of exceeding 6.0 kN was regarded as passing.
[table 1]

[0088]
[Table 2-1]

[0089]
[Table 2-2]

[0090]
[Table 2-3]

[0091]
[Table 3-1]

[0092]
[Table 3-2]

[0093]
[Table 3-3]

[0094]
[Table 4-1]

[0095]
[Table 4-2]

[0096]
[Table 4-3]

[0097]
[Table 5-1]

[0098]
[Table 5-2]

[0099]
[Table 5-3]

[0100]
 As described above, according to the present invention, it was confirmed that a steel sheet having both formability and weldability can be obtained by reforming the surface layer portion.
[0101]
 On the other hand, in the steel sheets of Comparative Examples 50 and 71, the wire diameter added in the continuous casting process is smaller than 1 mm, and the number density of Al oxides in the surface layer portion is below 3000 pieces/mm 2 . As a result, the weld joint strength was 6.0 kN or less.
[0102]
 In the steel sheets of Comparative Examples 51 and 73, the distance between the center position of the wire added in the continuous casting process and the molten steel surface is smaller than the wire diameter, and the number density of Al oxides in the surface layer portion is less than 3000 pieces/mm 2 . As a result, the weld joint strength was 6.0 kN or less.
[0103]
 In the steel sheets of Comparative Examples 52 and 72, the distance between the center position of the wire added in the continuous casting process and the surface of the molten steel is greater than the wire diameter + 30 mm, so the number density of Al oxides in the surface layer portion is less than 3000/mm 2 . and the number density of Al oxides exceeds 1000 pieces/mm 2 at a position half the plate thickness of the steel plate. As a result, the tensile strength×total elongation was less than 10000 MPa%, and the weld joint strength was 6.0 kN or less.
[0104]
 In the steel sheets of Comparative Examples 53 and 74, the distance between the wires added in the continuous casting process is larger than the wire diameter +30 mm, and the number density of Al oxides in the surface layer portion is smaller than 3000 pieces/mm 2 . As a result, the tensile strength x total elongation was 10000 MPa% or more, but the weld joint strength was 6.0 kN or less.
[0105]
 In the steel sheets of Comparative Examples 54 and 76, the difference between the feed speed of the wire added in the continuous casting process and the flow speed of the molten steel is greater than 500 mm/min, and the number density of Al oxides in the surface layer is less than 3000 pieces/mm 2 . . As a result, the tensile strength x total elongation was 10000 MPa% or more, but the weld joint strength was 6.0 kN or less.
[0106]
 In the steel sheets of Comparative Examples 55 and 61, the average cooling rate from 750°C to 550°C in the hot rolling process or annealing process is less than 2.5°C/s. As a result, these steel sheets have a tensile strength lower than 780 MPa.
[0107]
 In the steel sheets of Comparative Examples 57 and 58, the C concentration does not satisfy the requirements of this embodiment. As a result, these steel sheets do not meet the tensile strength or tensile strength x total elongation requirements.
[0108]
 The steel sheet of Comparative Example 59 has a tensile strength lower than 780 MPa because the heating temperature in the annealing step is lower than Ac3 point -50°C.
[0109]
 In the steel sheet of Comparative Example 60, the heating and holding time in the annealing step was shorter than 5 seconds, so the tensile strength was lower than 780 MPa, and the tensile strength×total elongation was less than 10000 MPa %.
[0110]
 In the steel sheets of Comparative Examples 67 and 70, the wire diameter added in the continuous casting process is larger than 50 mm, the number density of Al oxides in the surface layer is higher than 6000/mm 2 , and the average logarithmic value of the grain size is - Greater than 3.5. As a result, in the steel plate of this comparative example, the tensile strength×total elongation was less than 10000 MPa%, and the weld joint strength was 6.0 kN or less.
[0111]
 In the steel sheets of Comparative Examples 68 and 75, the distance between the wires added in the continuous casting process is smaller than the wire diameter, the number density of Al oxides in the surface layer is greater than 6000/mm 2 , and the logarithmic value of the grain size is is greater than -3.5. As a result, the tensile strength×total elongation was less than 10000 MPa%, and the welded joint strength was 6.0 kN or less.
[0112]
 In the steel sheets of Comparative Examples 69 and 77, the difference between the feed rate of the wire added in the continuous casting process and the flow rate of molten steel is less than -500 mm/min, and the number density of Al oxides in the surface layer is more than 6000 pieces/mm 2 . big. As a result, the tensile strength×total elongation was less than 10000 MPa%, and the welded joint strength was 6.0 kN or less.
Industrial applicability
[0113]
 ADVANTAGE OF THE INVENTION According to this invention, the steel plate which is excellent in formability and weldability can be provided. Such a steel sheet of the present invention is suitable for structural materials in the field of transportation equipment such as automobiles.
Code explanation
[0114]
 1 molten steel
 2 wire
 11 tundish
 12 continuous casting machine
The scope of the claims
[Claim 1]
 A steel plate having a tensile strength of 780 MPa or more, and
 when a region from the surface of the steel plate to 30 μm in the plate thickness direction is defined as a surface layer portion,  Al oxide particles having
 a particle size of 20 nm or more are included in the surface layer portion on at least one side. exists at a number density of
3000 to 6000/mm 2
,  and the natural logarithm of the particle size of the Al oxide particles measured in μm has an average of −5.0 to −3.5 and a standard deviation of 0.5. 8 or less, and the number of Al oxide particles in which the deviation of the natural logarithm of the particle size from the average is more than twice the standard deviation is 5% or less of the total number of Al oxide particles having a particle size of 20 nm or more. The chemical composition at a position 1/4 of the plate thickness from the surface of the
 steel plate is, in mass%,
 C: 0.050 to 0.800%,
 Si: 0.01 to 1.20%,
 Mn: 0 .01 to 8.00%,
 P: 0.100% or less,
 S: 0.050% or less,
 Al: 0 to 3.000%,
 N: 0.010% or less,
 O: 0 to 0.20%,
 Cr: 0-3.00%,
 Mo: 0-1.00%,
 B: 0-0.0100%,
 Ti: 0-0.200%,
 Nb: 0 to 0.200%,
 V: 0 to 0.20%,
 Cu: 0 to 1.000%,
 Ni: 0 to 1.000%,
 balance: Fe and impurities
, 1 of the thickness of the steel sheet A steel sheet , wherein the number density of Al oxide particles is 1000/mm 2 or less at positions of /2.
[Claim 2]
 The chemical composition, in mass %, is
 Cr: 0.01 to 3.00%,
 Mo: 0.01 to 1.00%,
 B: 0.001 to 0.0100%,
 Ti: 0.010 to 0.00%. 200%,
 Nb: 0.010-0.200%,
 V: 0.01-0.20%,
 Cu: 0.010-1.000%, and Ni
 : 0.010-1.000%
The steel sheet according to claim 1, comprising at least one selected from
[Claim 3]
 The steel sheet according to claim 1 or 2, wherein the metal structure at a position of 1/4 of the sheet thickness from the surface of the steel sheet contains retained austenite at an area ratio of 10% or more.
[Claim 4]
 The steel sheet according to any one of claims 1 to 3, further comprising a hot-dip galvanized layer, an alloyed hot-dip galvanized layer, or an electro-galvanized layer on the surface of the surface layer portion.

Documents

Application Documents

# Name Date
1 202117041374-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [14-09-2021(online)].pdf 2021-09-14
2 202117041374-STATEMENT OF UNDERTAKING (FORM 3) [14-09-2021(online)].pdf 2021-09-14
3 202117041374-PROOF OF RIGHT [14-09-2021(online)].pdf 2021-09-14
4 202117041374-PRIORITY DOCUMENTS [14-09-2021(online)].pdf 2021-09-14
5 202117041374-POWER OF AUTHORITY [14-09-2021(online)].pdf 2021-09-14
6 202117041374-NOTIFICATION OF INT. APPLN. NO. & FILING DATE (PCT-RO-105-PCT Pamphlet) [14-09-2021(online)].pdf 2021-09-14
7 202117041374-FORM 1 [14-09-2021(online)].pdf 2021-09-14
8 202117041374-DRAWINGS [14-09-2021(online)].pdf 2021-09-14
9 202117041374-DECLARATION OF INVENTORSHIP (FORM 5) [14-09-2021(online)].pdf 2021-09-14
10 202117041374-COMPLETE SPECIFICATION [14-09-2021(online)].pdf 2021-09-14
11 202117041374-MARKED COPIES OF AMENDEMENTS [06-10-2021(online)].pdf 2021-10-06
12 202117041374-MARKED COPIES OF AMENDEMENTS [06-10-2021(online)]-1.pdf 2021-10-06
13 202117041374-FORM 13 [06-10-2021(online)].pdf 2021-10-06
14 202117041374-AMMENDED DOCUMENTS [06-10-2021(online)].pdf 2021-10-06
15 202117041374.pdf 2021-10-23
16 202117041374-FORM 3 [07-01-2022(online)].pdf 2022-01-07
17 202117041374-FORM 18 [14-04-2023(online)].pdf 2023-04-14
18 202117041374-FER.pdf 2023-04-25
19 202117041374-Verified English translation [19-07-2023(online)].pdf 2023-07-19
20 202117041374-OTHERS [23-10-2023(online)].pdf 2023-10-23
21 202117041374-FER_SER_REPLY [23-10-2023(online)].pdf 2023-10-23
22 202117041374-DRAWING [23-10-2023(online)].pdf 2023-10-23
23 202117041374-CLAIMS [23-10-2023(online)].pdf 2023-10-23
24 202117041374-ABSTRACT [23-10-2023(online)].pdf 2023-10-23
25 202117041374-US(14)-HearingNotice-(HearingDate-30-05-2024).pdf 2024-04-30
26 202117041374-FORM-26 [22-05-2024(online)].pdf 2024-05-22
27 202117041374-Correspondence to notify the Controller [22-05-2024(online)].pdf 2024-05-22
28 202117041374-Written submissions and relevant documents [14-06-2024(online)].pdf 2024-06-14
29 202117041374-PatentCertificate18-06-2024.pdf 2024-06-18
30 202117041374-IntimationOfGrant18-06-2024.pdf 2024-06-18

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