Abstract: A steel sheet having a predetermined component composition satisfying formula (1), wherein a microstructure existing at a location 1/4 of the sheet thickness from the surface in the sheet thickness direction includes, in vol%, 95% or more of ferrite and 5% or less of remaining structures, the proportion of non-recrystallized ferrite in said ferrite is 5% or less, and X-ray wavelength ? and half width w at a peak representing the (200) plane of said ferrite satisfy formula (2). (1): 0.80={(Ti/48-N/14)+Nb/93}/(C/12)=5.00 (2): w×?=0.20
Title of invention : Steel plate and its manufacturing method
Technical field
[0001]
The present invention relates to a steel plate and a manufacturing method thereof.
This application claims priority based on Japanese Patent Application No. 2020-001529 filed in Japan on January 8, 2020, the content of which is incorporated herein.
Background technology
[0002]
In recent years, high-strength steel has been used in automobiles to reduce the weight of the vehicle body, improve fuel efficiency, and reduce carbon dioxide emissions, as well as to absorb collision energy during a collision to ensure the protection and safety of passengers. Steel plates are often used. However, in general, increasing the strength of a steel sheet lowers its deformability (ductility, bendability, etc.).
[0003]
For example, Patent Document 1 discloses a high-strength steel sheet with a tensile strength of 900 MPa or more that can achieve both high strength and excellent formability. In Patent Document 1, in the steel structure, in terms of area ratio, ferrite is 5% or more and 80% or less, autotempered martensite is 15% or more, bainite is 10% or less, and retained austenite is 5% or less, as quenched. of the martensite is 40% or less, the average hardness of the autotempered martensite is HV ≤ 700, and the average number of precipitated iron-based carbides of 5 nm or more and 0.5 µm or less in the autotempered martensite is 5 per 1 mm 2 ×10 4 or more.
[0004]
Patent Document 2 discloses a thin steel sheet that has a tensile strength of 900 MPa or more, good weldability, and good elongation. In the steel sheet of Patent Document 2, the area ratio of ferrite is 25% or more and 65% or less, the area ratio of martensite in which iron-based carbides are precipitated in martensite grains is 35% or more and 75% or less, and the remaining structure is the ferrite and The total area ratio is 20% or less (including 0%) other than the martensite, the average grain size of the ferrite and the martensite is 5 μm or less, and Si on the interface between the ferrite and the martensite and Mn having a steel structure with an atomic concentration of 5% or more.
[0005]
In Patent Document 3, a total of 60 area % or more of ferrite and bainite and 3 area % or more and 20 area % or less of retained austenite are contained, and the average grain size of the ferrite and bainite is 0.5 μm or more and 6.0 μm. Hereinafter, a Mn-enriched portion extending in the rolling direction at a depth of 50 μm from the steel plate surface and having a steel structure in which the C concentration in the retained austenite is 0.5% by mass or more and 1.2% by mass or less, and It has an element concentration distribution in which the average spacing of the Si-enriched parts in the direction perpendicular to the rolling direction is 1000 μm or less, the maximum depth of cracks on the steel sheet surface is 4.5 μm or less, and the width is 6 μm or less and the depth is 2 μm or more. The work hardening index (n 3-8 ) is 0.10 or more and bendability satisfies the formula (R/t≦1.5).
[0006]
Here, steel sheets for outer panels used for automobile side panels, hoods, etc. are required to have excellent dent resistance. In order to improve the dent resistance, it is effective to increase the yield strength and increase the strength. On the other hand, when performing press forming, it is necessary to lower the yield strength in order to suppress the occurrence of surface strain and ensure high surface accuracy. A bake hardening steel sheet (BH steel sheet) has been developed as a steel sheet that satisfies such contradictory requirements and achieves both press formability and high strength.
[0007]
This BH steel sheet is a steel sheet whose yield strength is increased by subjecting it to paint baking treatment including high-temperature heating and high-temperature holding after press forming. A BH steel sheet needs to have excellent bake hardenability (BH property) so that the yield strength increases after the paint baking treatment. In particular, there is a demand to introduce greater strain than before in steel sheets for outer panels, such as forming complex shapes to reduce the weight of the car body. A steel material that possesses is required.
[0008]
As a result of investigation by the present inventors, it was found that in Patent Documents 1 to 3, the bake hardenability (BH property) may not be sufficient.
prior art documents
patent literature
[0009]
Patent Document 1: International Publication No. 2009/096596
Patent Document 2: International Publication No. 2018/030503
Patent Document 3: Japanese Patent No. 5659929
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0010]
As described above, the present invention has been made in view of the fact that steel sheets are required to have improved BH properties in the high strain range in addition to improved formability. The present invention provides steel sheets (including zinc-coated steel sheets, zinc-alloy-coated steel sheets, alloyed zinc-coated steel sheets, and alloyed zinc-alloy-coated steel sheets) having excellent formability and BH properties in a high strain range, and a method for producing the same. intended to provide
Means to solve problems
[0011]
The gist of the present invention is as follows.
[1] A steel sheet according to an aspect of the present invention has a chemical composition, in mass%,
C: 0.0003 to 0.0100%,
Si: 0.005 to 1.500%,
Mn: 0.010 to 3.000%,
Al: 0.005 to 1.000%,
P: 0.100% or less,
S: 0.0200% or less,
N: 0.0150% or less,
O: 0.0100% or less,
V: 0 to 0.50%,
Cr: 0 to 1.00%,
Ni: 0 to 1.00%,
Cu: 0 to 1.00%,
Mo: 0 to 1.00%,
W: 0 to 1.00%,
B: 0 to 0.0100%,
Sn: 0 to 1.00%,
Sb: 0-0.20%, and
one or more of Ca, Ce, Mg, Zr, La and REM: 0 to 0.0100%,
contains
Ti: 0.010 to 0.100%, and
Nb: 0.005 to 0.060% containing one or two types,
satisfies the following formula (1),
The balance consists of Fe and impurities,
The microstructure at the 1/4 position of the plate thickness in the plate thickness direction from the surface is
By volume %, ferrite: 95% or more, residual structure: 5% or less,
The ratio of non-recrystallized ferrite in the ferrite is 5% or less,
The half width w and the X-ray wavelength λ at the peak of the (200) plane of the ferrite satisfy the following formula (2).
0.80≦{(Ti/48−N/14)+Nb/93}/(C/12)≦5.00 (1)
w×λ≧0.20 (2)
Ti, N, Nb and C in the above formula (1) indicate the content in mass% of each element, and 0 is substituted when the element is not contained.
[2] In the steel sheet according to (1) above, the chemical composition is, in mass%,
V: 0.01 to 0.50%,
Cr: 0.05 to 1.00%,
Ni: 0.05 to 1.00%,
Cu: 0.05 to 1.00%,
Mo: 0.03 to 1.00%,
W: 0.03 to 1.00%,
B: 0.0005 to 0.0100%,
Sn: 0.01 to 1.00%,
Sb: 0.005-0.20%, and
Total of one or more of Ca, Ce, Mg, Zr, La and REM: 0.0001 to 0.0100%
It may contain one or more selected from the group consisting of.
[3] In the steel sheet described in (1) or (2) above, the ferrite contained in the microstructure may have an average grain size of 6.0 to 15.0 μm.
[4] The steel sheet according to any one of (1) to (3) above may have a galvanized layer on the surface.
[5] The steel sheet according to any one of (1) to (3) above may have a zinc alloy plating layer on the surface.
[6] In the steel sheet according to (4) or (5) above, the Fe content in the zinc plating layer or the zinc alloy plating layer is 7.0 to 13.0% by mass. good.
[7] A method for manufacturing a steel sheet according to another aspect of the present invention comprises:
A method for manufacturing the steel sheet according to any one of (1) to (3) above,
A steel slab having the chemical composition described in (1) above is heated to 1200 to 1320 ° C., hot rolling is completed so that the hot rolling completion temperature is 880 ° C. or higher, and the hot rolling completion temperature is 500 ° C. A hot rolling step of cooling the hot rolled steel sheet so that the average cooling rate in the temperature range is 20 ° C./s or more;
a reheating step of heating the hot-rolled steel sheet to a temperature range of 500 to 700°C;
a cooling step of cooling the hot-rolled steel sheet to room temperature;
A cold-rolling step of cold-rolling the hot-rolled steel sheet so that the total rolling reduction is 60 to 90% and the cold-rolling completion temperature is 250°C or less to obtain a cold-rolled steel sheet;
An annealing step of heating the cold-rolled steel sheet to an annealing temperature of 700 to 850°C and cooling it to a temperature range of 80°C or less;
and a temper rolling step of temper rolling the cold-rolled steel sheet so that the total rolling reduction is 0.05 to 2.00%,
In the reheating process,
In the temperature range of 500 to 700°C, the following formula (3) is satisfied,
In the annealing process,
In the heating process to the annealing temperature,
In the temperature range from 700°C to the annealing temperature, the following formula (4) is satisfied,
In the cooling process from the annealing temperature,
In the temperature range of 500 to 700°C, the following formula (5) is satisfied,
Bending is performed in a temperature range of 80 to 500°C while applying a tension of 20 MPa or more.
[Number 1]
In the above formula (3), K 20 is the carbonitriding of Ti and / or Nb in the 20th section when the temperature history in the temperature range of 500 to 700 ° C. in the reheating process is equally divided into 20 times. It is an index showing the degree of progress of deposition of substances. t n and K n are calculated by dividing the temperature history in the temperature range of 500 to 700 ° C in the reheating process by 20 equally with respect to time, and taking the average temperature in the n-th interval as T n [° C]. is. Δt K is the time [hr. ] represents. C, Nb and Ti represent the content [% by mass] of each element. However, t1=ΔtK.
[Number 2]
In the above formula (4), R i is the degree of progress of recrystallization in the temperature range from 700 ° C. to the annealing temperature, and the amount of C from Ti and / or Nb carbonitrides present at the grain boundaries to the grains. It is an index that indicates the progress of diffusion. R m is obtained by dividing the temperature history of the steel sheet from 700 ° C. to the annealing temperature in the heating process of the annealing process into 10 equal parts with respect to time, and taking the average temperature in the m-th section as T m [° C.]. It is calculated. Δt R represents the time [seconds] obtained by dividing the total residence time in the temperature range from 700° C. to the annealing temperature by 10. K20 is the value obtained by the above equation (3). A and B are constant terms, A is 9.67×10 9 and B is 1.25×10 4 .
[Number 3]
In the above formula (5), Pj is an index that indicates the progress of precipitation of C in the temperature range of 700 to 500°C. In the cooling process of the annealing process, P k divides the temperature history of the steel sheet from reaching 700 ° C. to reaching 500 ° C. into 10 times, and the average temperature in the k-th section is T It is calculated as k [°C]. Δt P represents the time [seconds] obtained by dividing the total staying time in the same temperature range by 10. R10 is a value obtained by substituting 10 for m of Rm in formula (4). D, E and F are constant terms, D is 4.47×10 4 , E is 2.11×10 0 and F is 1.25×10 4 .
[8] In the method for manufacturing a steel sheet according to (7) above, the cold-rolled steel sheet may be hot-dip galvanized in the cooling process of the annealing process.
[9] In the method for manufacturing a steel sheet according to (7) above, the cold-rolled steel sheet may be subjected to a hot-dip zinc alloy plating treatment in the cooling process of the annealing process.
[10] In the steel sheet manufacturing method according to (8) or (9) above, in the cooling process of the annealing step, alloying treatment may be performed after the hot dip galvanizing treatment or after the hot dip galvanizing treatment. good.
Effect of the invention
[0012]
According to the above aspect of the present invention, it is possible to provide a steel sheet with excellent formability and BH properties and a method for producing the same.
MODE FOR CARRYING OUT THE INVENTION
[0013]
Less than , the steel sheet according to the present embodiment and the method for manufacturing the same will be sequentially described. First, reasons for limiting the chemical composition (chemical composition) of the steel sheet according to the present embodiment will be described. In the numerical limits described below between "-", the lower limit and the upper limit are included in the range. Numerical values indicated as "less than" and "greater than" do not include the value within the numerical range. All % about component composition shows the mass %.
[0014]
The steel sheet according to the present embodiment has a chemical composition in mass% of C: 0.0003 to 0.0100%, Si: 0.005 to 1.500%, Mn: 0.010 to 3.000%, Al : 0.005 to 1.000%, P: 0.100% or less, S: 0.0200% or less, N: 0.0150% or less, O: 0.0100% or less, V: 0 to 0.50% , Cr: 0-1.00%, Ni: 0-1.00%, Cu: 0-1.00%, Mo: 0-1.00%, W: 0-1.00%, B: 0- 0.0100%, Sn: 0 to 1.00%, Sb: 0 to 0.20%, and the sum of one or more of Ca, Ce, Mg, Zr, La and REM: 0 to 0. 0100%, containing one or two of Ti: 0.010 to 0.100% and Nb: 0.005 to 0.060%, formula (1) (0.80 ≤ {(Ti/ 48−N/14)+Nb/93}/(C/12)≦5.00), and the balance consists of Fe and impurities. Each element will be described below.
[0015]
C: 0.0003-0.0100%
C is an element that greatly increases the strength of the steel sheet. If the C content is 0.0003% or more, sufficient tensile strength (maximum tensile strength) can be obtained, so the C content is made 0.0003% or more. In order to increase the tensile strength of the steel sheet, the C content is preferably 0.0005% or more, more preferably 0.0010% or more.
In addition, when the C content is 0.0100% or less, the generation of a large amount of retained austenite after heat treatment can be suppressed, and the BH property can be secured. Also, the formability of the steel sheet can be ensured. Therefore, the C content is made 0.0100% or less. In order to further improve the BH properties, the C content is preferably 0.0090% or less, more preferably 0.0080% or less.
[0016]
Si: 0.005-1.500%
Si is an element that refines iron-based carbides and contributes to improving the strength-formability balance. In order to improve the strength-formability balance, the Si content should be 0.005% or more. Preferably, it is 0.025% or more. In particular, from the viewpoint of increasing the strength, it is more preferable to set the content to 0.100% or more.
In addition, when the Si content is 1.500% or less, coarse Si oxides that act as fracture starting points are less likely to be formed, cracks are less likely to occur, and embrittlement of steel can be suppressed. Therefore, the Si content is set to 1.500% or less. The Si content is preferably 1.300% or less, more preferably 1.000% or less.
[0017]
Mn: 0.010 to 3.000%
Mn is an element that enhances the hardenability of steel and contributes to the improvement of strength. In order to obtain the desired strength, the Mn content should be 0.010% or more. Preferably, it is 0.050% or more, more preferably 0.200% or more.
In addition, when the Mn content is 3.000% or less, it is possible to suppress deterioration of formability of the steel sheet due to loss of macro homogeneity in the steel sheet due to uneven distribution of Mn during casting. When the Mn content is 3.000% or more, the Ac1 temperature of the steel is lowered, and the amount of ferrite formed in the annealing process is lowered, resulting in deterioration of formability. Therefore, the Mn content is set to 3.000% or less. In order to obtain better moldability, the Mn content is preferably 2.800% or less, more preferably 2.600% or less.
[0018]
Al: 0.005-1.000%
Al is an element that functions as a deoxidizer. If the Al content is 0.005% or more, a sufficient deoxidizing effect can be obtained, so the Al content is made 0.005% or more. It is preferably 0.010% or more, more preferably 0.020% or more.
Al is an element that forms coarse oxides that act as starting points for fracture and embrittles steel. When the Al content is 1.000% or less, it is possible to suppress the formation of coarse oxides that act as starting points of fracture, and to suppress the slab from becoming easily cracked. Therefore, the Al content is set to 1.000% or less. The Al content is preferably 0.800% or less, more preferably 0.600% or less.
[0019]
P: 0.100% or less
P is an element that embrittles the steel and embrittles the molten part generated by spot welding. When the P content is 0.100% or less, it is possible to prevent the steel sheet from becoming brittle and easily cracked during the production process. Therefore, the P content is set to 0.100% or less. From the viewpoint of productivity, the P content is preferably 0.050% or less, more preferably 0.030% or less.
Although the lower limit of the P content includes 0%, the lower limit may be 0.001% because the production cost can be further suppressed by setting the P content to 0.001% or more.
[0020]
S: 0.0200% or less
S is an element that forms Mn sulfide and deteriorates formability such as ductility, hole expandability, stretch flangeability and bendability. If the S content is 0.0200% or less, the formability of the steel sheet can be suppressed from significantly deteriorating, so the S content is made 0.0200% or less. The S content is preferably 0.0100% or less, more preferably 0.0080% or less.
Although the lower limit of the S content includes 0%, the lower limit may be 0.0001% because the manufacturing cost can be further suppressed by setting the S content to 0.0001% or more.
[0021]
N: 0.0150% or less
N is an element that forms nitrides and deteriorates formability such as ductility, hole expandability, stretch flangeability and bendability. If the N content is 0.0150% or less, it is possible to suppress deterioration in the formability of the steel sheet, so the N content is made 0.0150% or less. In addition, N is also an element that causes welding defects during welding and hinders productivity. Therefore, the N content is preferably 0.0120% or less, more preferably 0.0100% or less.
The lower limit of the N content includes 0%, but the production cost can be further suppressed by setting the N content to 0.0005% or more, so 0.0005% may be the lower limit.
[0022]
O: 0.0100% or less
O is an element that forms oxides and impairs formability such as ductility, hole expansibility, stretch flangeability and bendability. If the O content is 0.0100% or less, the formability of the steel sheet can be suppressed from significantly deteriorating, so the O content is made 0.0100% or less. It is preferably 0.0080% or less, more preferably 0.0050% or less.
The lower limit of the O content includes 0%, but by setting the O content to 0.0001% or more, the manufacturing cost can be further suppressed, so 0.0001% may be set as the lower limit.
[0023]
Ti: 0.010 to 0.100% and Nb: 1 or 2 types of 0.005 to 0.060%
Ti is an element that has the effect of reducing S, N, and O that generate coarse inclusions that act as starting points for fracture. In addition, Ti has the effect of refining the structure and improving the strength-formability balance of the steel sheet. Nb is an element that contributes to the improvement of steel sheet strength through strengthening by precipitates, grain refinement strengthening by suppressing the growth of ferrite grains, and dislocation strengthening by suppressing recrystallization. Furthermore, Ti and Nb form carbonitrides to fix carbon and nitrogen, thereby suppressing excessive remaining of solute carbon in ferrite grains. Moreover, the BH property of a steel plate can be improved by containing a desired amount of Ti or Nb. In order to obtain these effects, one or both of Ti and Nb are contained. In order to reliably obtain the above effect, one or two of Ti: 0.010% or more and Nb: 0.005% or more are contained. As long as Ti is contained in an amount of 0.010% or more or Nb is contained in an amount of 0.005% or more, there is no problem even if the other element is contained as an impurity in an amount less than the lower limit. If a predetermined amount of either Ti or Nb is not contained, the excessive remaining solute carbon may raise the yield point and cause yield elongation.
Also, when the Ti content is 0.100% or less, formation of coarse Ti sulfides, Ti nitrides, and Ti oxides can be suppressed, and deterioration of the formability of the steel sheet can be suppressed. Moreover, the proportion of non-recrystallized ferrite can be reduced, and the formability of the steel sheet can be ensured. Therefore, the Ti content is set to 0.100% or less. The Ti content is preferably 0.075% or less, more preferably 0.060% or less. When the Nb content is 0.060% or less, recrystallization can be promoted to suppress the remaining non-recrystallized ferrite, and the formability of the steel sheet can be ensured. Therefore, the Nb content is set to 0.060% or less. The Nb content is preferably 0.050% or less, more preferably 0.040% or less.
[0024]
The balance of the chemical composition of the steel sheet according to the present embodiment may be Fe and impurities. Examples of impurities include elements that are inevitably mixed from steel raw materials or scraps and/or during the steelmaking process and that are permissible within a range that does not impair the properties of the steel sheet according to the present embodiment. As impurities, H, Na, Cl, Co, Zn, Ga, Ge, As, Se, Tc, Ru, Rh, Pd, Ag, Cd, In, Te, Cs, Ta, Re, Os, Ir, Pt, Au , Pb, Bi, and Po. The total amount of impurities may be 0.100% or less.
[0025]
The steel sheet according to the present embodiment may contain the following elements as optional elements instead of part of Fe. The content is 0% when the following optional elements are not contained.
[0026]
V: 0 to 0.50%
V is an element that contributes to the improvement of steel sheet strength through strengthening by precipitates, grain refinement strengthening by suppressing the growth of ferrite grains, and dislocation strengthening by suppressing recrystallization. Since V does not necessarily have to be contained, the lower limit of the V content includes 0%. The V content is preferably 0.01% or more, and more preferably 0.03% or more, in order to sufficiently obtain the strength improvement effect of V.
In addition, when the V content is 0.50% or less, it is possible to suppress the deterioration of the formability of the steel sheet due to the precipitation of a large amount of carbonitrides. Therefore, the V content is set to 0.50% or less.
[0027]
Cr: 0-1.00%
Cr is an element that increases the hardenability of steel and contributes to the improvement of steel sheet strength, and is an element that can partially replace Mn. Since Cr does not necessarily have to be contained, the lower limit of the Cr content includes 0%. The Cr content is preferably 0.05% or more, more preferably 0.20% or more, in order to sufficiently obtain the strength improvement effect of Cr.
In addition, when the Cr content is 1.00% or less, it is possible to suppress the formation of coarse Cr carbides that can serve as starting points for fracture. Therefore, the Cr content is set to 1.00% or less.
[0028]
Ni: 0-1.00%
Ni is an element that suppresses phase transformation at high temperatures and contributes to the improvement of steel sheet strength, and is an element that can partially replace Mn. Since Ni does not necessarily have to be contained, the lower limit of the Ni content includes 0%. The Ni content is preferably 0.05% or more, more preferably 0.20% or more, in order to sufficiently obtain the strength improvement effect of Ni.
In addition, if the Ni content is 1.00% or less, deterioration of the weldability of the steel sheet can be suppressed, so the Ni content is made 1.00% or less.
[0029]
Cu: 0-1.00%
Cu is an element that exists in steel as fine particles and contributes to improving the strength of the steel sheet, and is an element that can partially replace C and/or Mn. Since Cu does not necessarily have to be contained, the lower limit of the Cu content includes 0%. The Cu content is preferably 0.05% or more, more preferably 0.15% or more, in order to sufficiently obtain the strength improvement effect of Cu.
Also, if the Cu content is 1.00% or less, it is possible to suppress deterioration of the weldability of the steel sheet, so the Cu content is made 1.00% or less.
[0030]
Mo : 0-1.00%
Mo is an element that suppresses phase transformation at high temperatures and contributes to the improvement of steel sheet strength, or is an element that can partially replace Mn. Since Mo does not necessarily have to be contained, the lower limit of the Mo content includes 0%. In order to sufficiently obtain the strength improvement effect of Mo, the Mo content is preferably 0.03% or more, more preferably 0.06% or more.
In addition, when the Mo content is 1.00% or less, it is possible to suppress the decrease in hot workability and productivity. Therefore, Mo content shall be 1.00% or less.
[0031]
W: 0-1.00%
W is an element that suppresses phase transformation at high temperatures and contributes to improvement of steel sheet strength, and is an element that can partially replace C and/or Mn. Since W does not necessarily have to be contained, the lower limit of the W content includes 0%. In order to sufficiently obtain the strength improvement effect of W, the W content is preferably 0.03% or more, more preferably 0.10% or more.
In addition, if the W content is 1.00% or less, it is possible to suppress the deterioration of hot workability and productivity, so the W content is made 1.00% or less.
[0032]
B: 0-0.0100%
B is an element that suppresses phase transformation at high temperatures and contributes to the improvement of steel sheet strength, and is an element that can partially replace Mn. Since B does not necessarily have to be contained, the lower limit of the B content includes 0%. The B content is preferably 0.0005% or more, more preferably 0.0010% or more, in order to sufficiently obtain the strength improvement effect of B.
In addition, if the B content is 0.0100% or less, it is possible to suppress the formation of B precipitates and the decrease in strength of the steel sheet, so the B content is made 0.0100% or less.
[0033]
Sn: 0-1.00%
Sn is an element that suppresses the coarsening of crystal grains and contributes to the improvement of steel sheet strength. Since Sn does not necessarily have to be contained, the lower limit of the Sn content includes 0%. In order to sufficiently obtain the effect of Sn, the Sn content is more preferably 0.01% or more.
Also, if the Sn content is 1.00% or less, the steel sheet can be prevented from embrittlement and breakage during rolling, so the Sn content is made 1.00% or less.
[0034]
Sb: 0-0.20%
Sb is an element that suppresses the coarsening of crystal grains and contributes to the improvement of steel sheet strength. Since Sb does not necessarily have to be contained, the lower limit of the Sb content includes 0%. In order to sufficiently obtain the above effects, the Sb content is preferably 0.005% or more.
Also, if the Sb content is 0.20% or less, the steel sheet can be prevented from embrittlement and breakage during rolling, so the Sb content is made 0.20% or less.
[0035]
One or more of Ca, Ce, Mg, Zr, La and REM: 0 to 0.0100% in total
The chemical composition of the steel sheet according to the present embodiment may contain one or more of Ca, Ce, Mg, Zr, La and REM, if necessary. Ca, Ce, Mg, Zr, La, and REM are elements that contribute to improving the formability of steel sheets. The lower limit of the sum of one or more of Ca, Ce, Mg, Zr, La and REM includes 0%, but the total is preferably 0.0001% or more in order to sufficiently obtain the effect of improving moldability, 0.0010% or more is more preferable.
Also, when the total content of one or more of Ca, Ce, Mg, Zr, La, and REM is 0.0100% or less, it is possible to suppress a decrease in ductility of the steel sheet. Therefore, the total content of the above elements is set to 0.0100% or less. Preferably, it is 0.0050% or less.
[0036]
REM (Rare Earth Metal) means a group of elements belonging to the lanthanide series, excluding individually specified La and Ce. These are often added in the form of misch metals, but may inevitably contain elements of the lanthanide series in addition to La and Ce.
[0037]
0.80≦{(Ti/48−N/14)+Nb/93}/(C/12)≦5.00 (1)
The chemical composition of the steel sheet according to this embodiment satisfies the above formula (1). By satisfying the above formula (1), it is possible to suppress the deterioration of the formability of the steel sheet and the deterioration of the BH property due to an increase in the amount of cementite in the microstructure.
It should be noted that Ti, N, Nb and C in the above formula (1) indicate the content in mass% of each element, and 0 is substituted when the element is not contained. Also, if the value (Ti/48−N/14) in parentheses including Ti and N is negative, 0 is substituted as the value in the parentheses.
[0038]
Next, the microstructure of the steel sheet according to this embodiment will be described.
The steel sheet according to the present embodiment contains, by volume%, ferrite: 95% or more and the remaining structure: 5% or less in the microstructure at the 1/4 position of the plate thickness in the plate thickness direction from the surface, and accounts for the ferrite. The ratio of unrecrystallized ferrite is 5% or less, and the half width w and X-ray wavelength λ (w is in degrees, λ is in Å) at the peak of the ferrite (200) plane satisfy the following formula (2) Fulfill.
In the present embodiment, the reason why the microstructure at the 1/4 position of the plate thickness is defined from the surface in the plate thickness direction is that the microstructure at this position indicates a typical microstructure of the steel plate and has a correlation with the mechanical properties of the steel plate. is strong. All ratios of the following structures in the microstructure are volume ratios.
[0039]
w×λ≧0.20 (2)
The unit of w×λ is "degree/Å".
[0040]
Ferrite: 95% or more
Ferrite is a structure with excellent formability. Desired formability can be obtained as the volume fraction of ferrite is 95% or more. Therefore, the volume fraction of ferrite is set to 95% or more. The volume fraction of ferrite is preferably 97% or more. Since more ferrite is preferable, the volume fraction of ferrite may be 100%.
The ferrite referred to here also includes non-recrystallized ferrite.
[0041]
Remaining organization: 5% or less
In this embodiment, the residual structure is a structure that deteriorates the formability of the steel sheet. Since the formability of the steel sheet can be ensured by setting the volume fraction of the residual structure to 5% or more, the volume fraction of the residual structure is set to 5% or less. Since the residual tissue does not have to exist, the volume fraction of the residual tissue may be 0%. The residual structure in this embodiment means acicular ferrite, massive ferrite, pearlite, bainite, martensite, and retained austenite.
[0042]
Proportion of non-recrystallized ferrite in ferrite: 5% or less
Non-recrystallized ferrite is ferrite in which the strain introduced by cold rolling or the like remains inside. Compared to ordinary ferrite, it has higher strength but lower ductility. Therefore, in the steel sheet according to the present embodiment, the ratio of non-recrystallized ferrite to ferrite is limited to 5% or less. The proportion of non-recrystallized ferrite in ferrite is preferably 3% or less, more preferably 1% or less. In order to improve the formability of the steel sheet, it is more preferable not to contain unrecrystallized ferrite, so the ratio of unrecrystallized ferrite to ferrite may be 0%.
[0043]
The method for measuring the volume fraction of ferrite will be described below.
A test piece is taken from a steel plate, with a cross section parallel to the rolling direction of the steel plate and perpendicular to the steel plate surface as the observation surface. After polishing the observation surface of the test piece, nital etching is performed. On the observation surface, in a region of t / 8 to 3 t / 8 (t is the plate thickness) from the surface so that the 1/4 position of the plate thickness in the plate thickness direction from the surface is the center, in one or more fields of view, A total area of 2.0×10 −9 m 2 or more is observed with a field emission scanning electron microscope (FE-SEM) at a magnification of 1000 to 3000 times.
[0044]
The ferrite is identified based on the morphology of the structure (crystal grain shape, carbide formation state, etc.) and its area ratio (area %) is measured. Specifically, a region in which the crystal grains are lath-shaped and a region in which a plurality of fine carbides having a major axis of 1.0 μm or less that can be observed at the above magnification are present in the crystal grains are regarded as structures other than ferrite. area is regarded as ferrite. The obtained area ratio of ferrite is regarded as the volume ratio of ferrite. This gives the volume fraction of ferrite. Note that the volume fraction of ferrite determined here also includes the volume fraction of non-recrystallized ferrite.
[0045]
When observing multiple fields of view, the area to be analyzed in each field of view shall be 4.0×10 −10 m 2 or more. The area ratio is measured by the point counting method in each field of view, 15 lines are drawn parallel to the rolling direction and 15 lines are drawn perpendicular to the rolling direction, and the structure is determined at 225 points of intersection of these lines.
[0046]
Average grain size of ferrite: 6.0 to 15.0 μm
In the above microstructure, the average grain size of ferrite is preferably 6.0 to 15.0 μm. By setting the average crystal grain size of ferrite to 6.0 to 15.0 μm, both high tensile strength and high formability can be obtained.
[0047]
The method for measuring the average grain size of ferrite and the ratio of non-recrystallized ferrite to ferrite will be described below.
In each of the above fields where the volume fraction of ferrite was measured, a maximum of 15 straight lines parallel to the rolling direction and a maximum of 15 straight lines perpendicular to the rolling direction were drawn, and the total length of the straight lines was 150 μm or more. Obtain the average grain size of ferrite.
[0048]
Furthermore, on the same observation surface as the observation surface on which the volume fraction of ferrite was measured, in a region of t / 8 to 3 t / 8 (t is the plate thickness) from the surface, in a field of view of 1 or more, a total of 4.0 × 10 For an area of −8 m 2 or more, the crystal orientation is analyzed using electron backscatter diffraction (EBSD) by FE-SEM. From the obtained crystal orientation map of bcc iron, the boundary with an orientation difference of 5.0 degrees or more is regarded as a grain boundary, and the grain orientation spread (GOS) within the grain is determined. Crystal grains of 0 degree or more are regarded as non-recrystallized ferrite, and the volume fraction is obtained. By dividing the obtained volume ratio of non-recrystallized ferrite by the volume ratio of ferrite, the ratio of non-recrystallized ferrite to ferrite is obtained. For analysis of crystal orientation, for example, OIM Data Collection and OIM Data Analysis manufactured by TSL can be used.
[0049]
In the ferrite of the present embodiment, the half-value width w and the X-ray wavelength λ (units of w and λ are Å) at the peak of the (200) plane of ferrite satisfy the formula (2) (w × λ ≥ 0.20)
Desired moldability and BH property can be obtained by satisfying the formula (2) for the half width w and the X-ray wavelength λ at the peak of the (200) plane of ferrite. The half-value width w increases when solid solution C or the like exists in the vicinity of the crystal grain boundary and distorts the crystal lattice. On the other hand, when coarse carbides are present at the grain boundaries, the crystal lattice is not distorted, so the half width w does not increase. The steel sheet according to the present embodiment has a large amount of dissolved C in the vicinity of the grain boundaries, so the half width w is large. Thereby, desired moldability and BH property can be obtained.
[0050]
A method for measuring the half width w at the peak of the (200) plane of ferrite will be described below.
A small piece of 25 mm x 25 mm x plate thickness is cut from the steel plate, and the plate surface of the test piece is mechanically polished to a position t/4 (t is the plate thickness) from the surface. Next, electrolytic polishing is performed to remove the distorted portion of the surface layer to obtain a mirror surface, and an X-ray diffraction pattern is obtained by performing an X-ray diffraction test using a Cu tube on the observed surface. From the figure, the peak of the (200) plane of bcc iron (ferrite) is read, the half width w and the wavelength λ at the peak are obtained, and the equation (2) is calculated.
[0051]
The steel sheet according to this embodiment may be a steel sheet having a zinc coating layer or a zinc alloy coating layer on one or both sides of the steel sheet. In addition, the steel sheet according to the present embodiment has an alloying treatment on the zinc coating layer or the zinc alloy coating layer.A steel sheet having a treated galvannealed layer or a galvannealed zinc alloy layer may also be used.
The plating layer formed on one or both sides of the steel sheet according to the present embodiment is preferably a zinc plating layer or a zinc alloy plating layer containing zinc as a main component. The zinc alloy plating layer preferably contains Ni as an alloy component.
[0052]
The zinc plating layer and zinc alloy plating layer are formed by hot dip plating, electroplating, or vapor deposition. When the Al content of the galvanized layer is 0.5% by mass or less, the adhesion between the steel sheet surface and the galvanized layer can be ensured, so the Al content of the galvanized layer is 0.5% by mass or less. is preferred. When the galvanized layer is a hot-dip galvanized layer, the amount of Fe in the hot-dip galvanized layer is preferably 3.0% by mass or less in order to increase the adhesion between the steel sheet surface and the galvanized layer.
When the galvanized layer is an electrogalvanized layer, the Fe content of the galvanized layer is preferably 0.5% by mass or less from the viewpoint of improving corrosion resistance.
[0053]
The zinc plating layer and the zinc alloy plating layer include Al, Ag, B, Be, Bi, Ca, Cd, Co, Cr, Cs, Cu, Ge, Hf, Zr, I, K, La, Li, Mg, Mn, One or more of Mo, Na, Nb, Ni, Pb, Rb, Sb, Si, Sn, Sr, Ta, Ti, V, W, Zr, and REM are added to a range that does not impair the corrosion resistance and formability of the steel sheet. may be contained in In particular, Ni, Al, and Mg are effective in improving corrosion resistance.
[0054]
The zinc coating layer or zinc alloy coating layer on the surface of the steel sheet according to the present embodiment may be a zinc alloy coating layer or zinc alloy coating layer that has undergone alloying treatment. When alloying the hot-dip galvanized layer or the hot-dip galvanized layer, the hot-dip galvanized layer after the alloying treatment (alloyed galvanized layer) is used from the viewpoint of improving the adhesion between the steel sheet surface and the alloyed coating layer. Alternatively, the Fe content of the hot-dip zinc alloy plating layer (alloyed zinc alloy plating layer) is preferably 7.0 to 13.0% by mass. By subjecting a steel sheet having a hot-dip galvanized layer or a hot-dip galvanized layer to an alloying treatment, Fe is incorporated into the galvanized layer and the Fe content is increased. Thereby, the Fe content can be made 7.0% by mass or more. That is, the zinc plating layer having an Fe content of 7.0% by mass or more is an alloyed zinc plating layer or an alloyed zinc alloy plating layer.
[0055]
The Fe content of the hot-dip galvanized layer (alloyed zinc-plated layer) or the hot-dip zinc alloy-plated layer (alloyed zinc-alloyed layer) after the alloying treatment can be obtained by the following method. Only the plated layer is dissolved and removed using a 5% by volume HCl aqueous solution containing an inhibitor. By measuring the Fe content in the obtained solution using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry), the Fe content (% by mass) in the galvanized layer is obtained.
[0056]
The plate thickness of the steel plate according to the present embodiment is not limited to a specific range, but considering versatility and manufacturability, it is preferably 0.2 to 5.0 mm. By setting the plate thickness to 0.2 mm or more, the steel plate shape can be easily maintained flat, and dimensional accuracy and shape accuracy can be improved. Therefore, the plate thickness is preferably 0.2 mm or more. More preferably, it is 0.4 mm or more.
In addition, by setting the plate thickness to 5.0 mm or less, it is possible to easily perform appropriate strain application and temperature control in the manufacturing process, and to obtain a homogeneous structure. Therefore, the plate thickness is preferably 5.0 mm or less. More preferably, it is 4.5 mm or less.
[0057]
The steel plate according to this embodiment preferably has a tensile strength of 270 MPa or more. More preferably, it is 300 MPa or more. Although the upper limit is not particularly limited, it may be, for example, 500 MPa or less.
The tensile strength is measured by preparing a No. 5 test piece according to JIS Z 2241:2011 and performing a tensile test with the tensile axis perpendicular to the rolling direction of the steel plate (C direction).
[0058]
Next, a method for manufacturing a steel plate according to this embodiment will be described.
The steel sheet according to the present embodiment can obtain the above effects regardless of the manufacturing method. However, the manufacturing method including the following steps is preferable because it can be stably manufactured. In the manufacturing method described below, a steel sheet having desired characteristics can be manufactured by comprehensively and inseparably controlling each step.
(I) Heat a steel slab having a predetermined chemical composition to 1200 to 1320 ° C., complete hot rolling so that the hot rolling completion temperature is 880 ° C. or higher, and heat the hot rolling completion temperature to 500 ° C. A hot-rolling step of cooling to a hot-rolled steel sheet by cooling so that the average cooling rate of the region is 20 ° C./s or more,
(II) a reheating step of heating the hot-rolled steel sheet to a temperature range of 500 to 700 ° C.;
(III) a cooling step of cooling the hot-rolled steel sheet to room temperature;
(IV) A cold-rolling step of cold-rolling the hot-rolled steel sheet to a cold-rolled steel sheet so that the total rolling reduction is 60 to 90% and the cold-rolling completion temperature is 250 ° C. or less;
(V) An annealing step of heating the cold-rolled steel sheet to an annealing temperature of 700 to 850° C. and cooling it to a temperature range of 80° C. or less;
(VI) A step of temper-rolling the cold-rolled steel sheet so that the total rolling reduction is 0.05 to 2.00%.
Preferred conditions for each step are described below.
[0059]
First, a cast slab having the chemical composition of the steel sheet according to the present embodiment described above is heated to 1200 to 1320°C. When the heating temperature is 1200° C. or higher, the carbides can be sufficiently dissolved, and by appropriately controlling the conditions of the intermediate steps described below, the unintentional formation of coarse carbides in the intermediate steps can be prevented. can be suppressed. As a result, the half width w and the X-ray wavelength λ can be set within desired ranges.
Also, if the heating temperature of the steel billet is 1320°C or less, the grain size can be made finer, and the anisotropy of the metal structure can be suppressed. In addition, the slab to be heated is preferably produced by continuous casting from the viewpoint of production cost, but may be produced by other casting methods (for example, ingot casting method).
[0060]
After heating the billet, hot rolling is applied so that the hot rolling completion temperature is 880°C or higher. When the hot rolling completion temperature is 880° C. or higher, the rolling is performed in the single phase region, so that the anisotropy of the microstructure can be suppressed. Also, the proportion of non-recrystallized ferrite can be reduced. Therefore, the hot rolling completion temperature is set to 880° C. or higher. The hot rolling completion temperature may be 1050° C. or lower.
[0061]
After the completion of hot rolling, the steel is cooled so that the average cooling rate in the temperature range from the hot rolling completion temperature to 500°C is 20°C/s or more. A hot-rolled steel sheet is thus obtained.
When the average cooling rate from the hot rolling completion temperature to 500 ° C. is 20 ° C./s or more, the formation of coarse Ti and / or Nb carbonitrides can be suppressed, and the desired microstructure is obtained in the finally obtained steel plate. Tissue is obtained.
Although the upper limit of the average cooling rate is not particularly set, since a special refrigerant is required to obtain a cooling rate exceeding 200 ° C./s, the average cooling rate is preferably 200 ° C./s or less from the viewpoint of production costs. . As long as the average cooling rate in the temperature range from the hot rolling completion temperature to 500°C is 20°C/s or more, the temperature at which cooling is stopped is not particularly specified.
[0062]
Note that the average cooling rate in this embodiment is a value obtained by dividing the temperature difference between the start point and the end point of the set range by the elapsed time from the start point to the end point.
[0063]
Next, the obtained hot-rolled steel sheet is heated to a temperature range of 500-700°C. In the reheating step, when the maximum reheating temperature (maximum heating temperature in the reheating step) is 500 to 700° C., a desired microstructure can be obtained, and moldability and BH property can be secured.
[0064]
Also, in the reheating process, the temperature history in the temperature range of 500 to 700°C must satisfy the following formula (3). In the following formula (3), K 20 is the carbonitriding of Ti and / or Nb in the 20th section when the temperature history in the above temperature range of 500 to 700 ° C. in the reheating process is equally divided into 20 with respect to time. It is an index showing the degree of progress of deposition of substances. When the temperature history in the temperature range of 500 to 700° C. satisfies the following formula (3), fine Ti and/or Nb carbonitrides are uniformly precipitated in the steel. Thereby, a desired microstructure can be obtained and the BH properties can be secured.
[0065]
[Number 4]
[0066]
[ °C]. Δt K is the time [hr. ], and C, Nb and Ti represent the content [% by mass] of each element. However, t1=ΔtK. log10 is the base 10 common logarithm.
[0067]
After the reheating process, the hot-rolled steel sheet is cooled to room temperature. The cooling rate at this time is not particularly limited, and cooling methods include air cooling and the like. For example, room temperature is 25° C., and the average cooling rate during air cooling is 10° C./s or less.
[0068]
Next, the hot-rolled steel sheet after cooling is cold-rolled so that the total rolling reduction is 60-90% and the cold-rolling completion temperature is 250°C or less. A cold-rolled steel sheet is thus obtained. When the total rolling reduction during cold rolling is 60% or more, recrystallization in the subsequent heat treatment can be sufficiently progressed, remaining non-recrystallized ferrite can be suppressed, and a desired microstructure can be obtained. Therefore, the total rolling reduction during cold rolling is set to 60% or more. The total rolling reduction is preferably 65% or more, more preferably 70% or more, from the viewpoint of refining the structure and enhancing the strength-formability balance. Further, when the total rolling reduction in cold rolling is 90% or less, it is possible to suppress an increase in the anisotropy of the steel sheet, reduce the proportion of non-recrystallized ferrite, and ensure formability. Therefore, the total rolling reduction during cold rolling is set to 90% or less. In order to further improve formability, the total rolling reduction is preferably 85% or less.
[0069]
In cold rolling, the temperature of the steel sheet rises due to heat generated during processing. If the temperature of the steel sheet is excessively high, the accumulation of work strain does not proceed sufficiently, the progress of recrystallization is inhibited, and an excessive amount of non-recrystallized ferrite remains in the finally obtained steel sheet. Therefore, the rolling reduction and the time between passes are controlled so that the temperature of the steel sheet at the completion of cold rolling (cold rolling completion temperature) is 250° C. or lower. From the standpoint of formability, the temperature at which cold rolling is completed is preferably 200° C. or lower in order to promote recrystallization efficiently. The cold rolling completion temperature may be 50° C. or higher. This is because cracking of the steel sheet during rolling can be further suppressed.
[0070]
[Heating process]
Subsequently, the cold rolled steel sheet after cold rolling is heat treated (annealed). First, a cold-rolled steel sheet is heated to an annealing temperature of 700-850°C. During this heating, the temperature history in the temperature range from 700° C. to the annealing temperature (700 to 850° C.) must satisfy the following formula (4). R i in the following formula (4) is the degree of progress of recrystallization in the temperature range from 700 ° C. to the annealing temperature and the diffusion of C from Ti and / or Nb carbonitrides present at the grain boundaries into the grains. It is an index that indicates the degree of progress of Heating is performed so that the temperature history in the temperature range from 700 ° C. to the annealing temperature satisfies the following formula (4), thereby promoting recrystallization of ferrite and carbonitriding Ti and / or Nb present at the grain boundaries. Diffusion of C from the material into grains. At this time, the diffusion of C in carbides present at grain boundaries progresses faster than the diffusion of C in carbides present in grains. Therefore, the size of Ti and/or Nb carbonitrides present at the grain boundaries is reduced. As a result, a desired microstructure can be obtained, and moldability and BH properties can be secured.
[0071]
[Number 5]
[0072]
In the above formula (4), Rm is the temperature history of the steel sheet from 700°C until it reaches the annealing temperature in the heating process of the annealing process., and the average temperature in the m-th interval is calculated as Tm [°C]. Δt R represents the time [seconds] obtained by dividing the total residence time in the same temperature range (700° C. to annealing temperature) by 10, and K 20 is the value obtained from the above formula (3). Also, A and B are constant terms, A being 9.67×10 9 and B being 1.25×10 4 .
[0073]
The annealing temperature in the annealing process should be 700°C or higher. When the annealing temperature is 700° C. or higher, the carbides can be sufficiently melted and a desired microstructure can be obtained. The annealing temperature is preferably 750°C or higher, more preferably 780°C or higher. Further, when the annealing temperature is 850° C. or lower, excessive dissolution of carbides and accelerated precipitation during the subsequent cooling process can be suppressed, and sufficient BH properties can be ensured. Therefore, the annealing temperature is set to 850° C. or lower. When the volume fraction of ferrite is increased to further improve formability, the annealing temperature is preferably 830° C. or lower, more preferably 810° C. or lower.
[0074]
[Holding process]
The holding time at the annealing temperature, that is, the time from reaching the annealing temperature of 700° C. or higher in the heating process to reaching 700° C. again after holding the annealing temperature of 700 to 850° C. shall be 3 seconds or longer. is preferred. By setting the holding time to 3 seconds or more, the carbide can be sufficiently dissolved, and formability can be ensured. The holding time is preferably 10 seconds or longer, more preferably 25 seconds or longer. Although the upper limit of the holding time is not particularly set, even if the holding time exceeds 200 seconds, the influence on the BH property of the steel sheet is small.
[0075]
[Cooling process]
After heating to the annealing temperature and securing the holding time, cool it.
In the cooling process, the temperature history satisfies the following formula (5) in the temperature range of 500-700°C, and bending is performed while applying a tension of 20 MPa or more in the temperature range of 80-500°C.
By performing cooling in which the temperature history in the temperature range of 500 to 700 ° C. satisfies the following formula (5), part of the C diffused in the crystal grains during the heating process carbonitrides Ti and / or Nb at the grain boundaries. The remaining C moves to the grain boundary in a solid solution state. As a result, a desired microstructure can be obtained, and moldability and BH properties can be secured. Pj in the following formula (5) is an index indicating the progress of precipitation of C in the temperature range of 700 to 500°C.
[0076]
[Number 6]
[0077]
In the cooling process of the annealing process, P k in the above formula (5) divides the temperature history of the steel sheet from reaching 700 ° C. to reaching 500 ° C. into 10 equal parts, is calculated as T k [° C.], which is the average temperature in the section of . Δt P represents the time [seconds] obtained by dividing the total staying time in the same temperature range by 10. R10 is a value obtained by substituting 10 for m of Rm in formula (4). D, E and F are constant terms, D is 4.47×10 4 , E is 2.11×10 0 and F is 1.25×10 4 .
[0078]
In the cooling process of the annealing step, after cooling is performed so that the temperature history in the temperature range of 500 to 700 ° C. satisfies the above formula (5), Ti and / or Nb carbonitrides and Solute C is present. If solute C exists in the grain boundaries, the dislocations existing in the grain boundaries are fixed by the solute C, so that the yield strength of the steel sheet increases, which is not preferable. Therefore, in a temperature range of 80 to 500° C., bending is performed while applying a tension of 20 MPa or more, so that solid solution C present in the grain boundaries is moved to the vicinity of the grain boundaries together with dislocations. However, in this state, the dislocations that have moved are fixed by solid solution C, so that the yield strength is high. As bending, for example, a method of performing roll bending using a metal roll having a diameter of 100 to 800 mm can be considered.
[0079]
The cold-rolled steel sheet after the above bending is subjected to temper rolling so that the total rolling reduction is 0.05 to 2.00%. By performing skin pass rolling, dislocations are moved from the dislocations moved to the vicinity of the grain boundary by bending and from solid solution C. As a result, the solute C can be removed from the dislocations while allowing the solute C to exist in the vicinity of the grain boundary. Therefore, a desired microstructure can be obtained, and as a result, desired BH property and yield strength can be obtained. When the total rolling reduction of temper rolling is 0.05% or more, dislocations can be moved from C, and sufficient BH properties can be secured. Further, when the total rolling reduction of temper rolling is 2.00% or less, excessive increase in yield strength can be suppressed.
[0080]
In this embodiment, the steel sheet may be subjected to hot-dip galvanizing treatment or hot-dip galvanizing treatment in the temperature range of 80 to 500° C. while bending or after bending. At this time, the steel sheet may be reheated before being immersed in the plating bath. Alternatively, the plated steel sheet may be heated to alloy the plated layer.
[0081]
A galvanized steel sheet having a galvanized layer is produced by subjecting the steel sheet after the annealing process to electroplating, or subjecting the steel sheet before temper rolling to vapor deposition treatment to form a galvanized layer on one or both sides of the steel sheet. good too.
The atmosphere in the annealing process may be controlled to modify the surface of the steel sheet. For example, by heat-treating in a decarburizing atmosphere, a steel sheet having excellent bendability in which the surface layer of the steel sheet is moderately decarburized can be obtained.
Example
[0082]
Next, examples of the present invention will be described, but the conditions in the examples are examples of conditions adopted to confirm the feasibility and effect of the present invention. The present invention is not limited to this one conditional example. Various conditions can be adopted in the present invention as long as the object of the present invention is achieved without departing from the gist of the present invention.
[0083]
A slab was produced by casting molten steel having the chemical composition shown in Tables 1-1 and 1-2. Next, hot rolling was performed under the conditions shown in Tables 2-1 and 2-2. First, the slab is heated to the billet heating temperature shown in Tables 2-1 and 2-2, and then hot-rolled in the temperature range up to the rolling completion temperature shown in Tables 2-1 and 2-2. After applying, the hot-rolled steel sheet was obtained by cooling from the rolling completion temperature to 500 ° C. at the average cooling rate shown in Tables 2-1 and 2-2. Next, the hot-rolled steel sheets were reheated under the conditions shown in Tables 2-1 and 2-2. Tables 2-1 and 2-2 show K 20 obtained from the temperature history in the temperature range of 500 to 700° C. in this reheating step. This K20 can be obtained by equation (3). After reheating, it was cooled to room temperature (25° C.) at an average cooling rate of 10° C./s or less.
[0084]
Subsequently, from the plate thickness before rolling to the plate thickness after rolling described in Tables 3-1 and 3-2, cold rolling is performed so that the rolling completion temperature described in Tables 3-1 and 3-2 is obtained. Thus, a cold-rolled steel sheet was obtained. The obtained cold-rolled steel sheets were annealed as shown in Tables 3-1 and 3-2. Annealing was performed by heating to the annealing temperature shown in Tables 3-1 and 3-2 and holding for 3 to 200 seconds (that is, after reaching an annealing temperature of 700 ° C. or higher during the heating process, annealing at 700 to 850 ° C. The time required to reach 700° C. again after holding the temperature was 3 to 200 seconds), and then cooled. In the cooling process of cooling to a temperature range of 80° C. or lower, bending was performed while applying the tension shown in Tables 3-1 and 3-2. After that, steel sheets were obtained by performing temper rolling at the total rolling reductions shown in Tables 3-1 and 3-2.
[0085]
In the bending process in the cooling process of the annealing process, roll bending was performed using a metal roll having a diameter of 100 mm in Experimental Examples 4 to 19, a diameter of 800 mm in Experimental Examples 39 to 54, and a diameter of 500 mm in other Experimental Examples. . Some of the steel sheets were subjected to hot-dip galvanizing treatment or hot-dip galvanizing treatment in the temperature range of 80 to 500° C. in the cooling process of the annealing process while bending or after bending. Steel sheets subjected to hot-dip galvanizing treatment or hot-dip galvanizing treatment were subjected to alloying treatment as necessary. In addition, some of the steel sheets were electroplated or vapor-deposited after the annealing process.
[0086]
The plating treatments in Tables 3-1 and 3-2 are as follows.
Zn alloy: After cooling the steel sheet to a temperature range of 500°C or less in the annealing process, it is immersed in a molten zinc alloy bath and cooled to room temperature to obtain a zinc alloy plated steel sheet.
Alloyed Zn alloy: In the annealing process, the steel sheet is cooled to a temperature range of 500 ° C. or less, immersed in a molten zinc alloy bath, subjected to alloying treatment by reheating to 580 ° C., and then cooled to room temperature to alloy. This is a process to obtain a zinc alloy plated steel sheet.
GA: In the annealing process, the steel sheet is cooled to a temperature range of 500°C or less, immersed in a molten zinc bath, subjected to alloying treatment by reheating to 560°C, and then cooled to room temperature to form an alloyed hot-dip galvanized steel sheet. (GA) is obtained.
GI: After cooling the steel sheet to a temperature range of 500°C or less in the annealing process, it is immersed in a molten zinc bath and cooled to room temperature to obtain a hot-dip galvanized steel sheet (GI).
Vapor deposition: A process to obtain a galvanized steel sheet by performing vapor deposition plating after temper rolling.
EG: After the annealing process, electrogalvanizing is applied to obtain an electrogalvanized steel sheet (EG).
[0087]
Tables 3-1 and 3-2 list ΣR i obtained from the temperature history in the temperature range from 700 to the annealing temperature in the heating process up to the annealing temperature. This ΣR i can be obtained by equation (4). Also, Tables 3-1 and 3-2 describe R 10·ΣP j obtained from the temperature history in the temperature range of 500 to 700° C. in the cooling process from the annealing temperature. This R 10·ΣP j can be obtained by Equation (5).
[0088]
Tables 4-1 and 4-2 show the characteristics of steel sheets obtained under the manufacturing conditions listed in Tables 1-1 to 3-2. Tables 4-1 and 4-2 show the volume fraction of ferrite, the proportion of non-recrystallized ferrite in ferrite, and the average grain size of ferrite as the results of structure observation conducted by the above method. In addition, w×λ (unit is “degree/Å”) is shown as a result of the X-ray diffraction test performed by the above-described method. The ratio of non-recrystallized ferrite to ferrite was measured using OIM Data Collection and OIM Data Analysis manufactured by TSL. The thickness of the steel plate was the same value as the thickness after rolling in Tables 3-1 and 3-2.
[0089]
For alloyed steel sheets, measure the Fe content of the hot-dip galvanized layer (alloyed zinc-coated layer) or hot-dip zinc alloy-coated layer (alloyed zinc-alloyed layer) by the method described above. did.
[0090]
The plating layers in Tables 4-1 and 4-2 are as follows.
Zn alloy: Zinc alloy plating layer
Alloyed Zn alloy: Alloyed zinc alloy plating layer
GA: An alloyed hot-dip galvanized layer formed by alloying after being immersed in a hot-dip zinc bath
GI: Hot-dip galvanized layer formed by immersion in a hot-dip zinc bath
Vapor deposition: Zinc plating layer formed by vapor deposition plating
EG: Galvanized layer formed by electrogalvanizing
[0091]
Tables 4-1 and 4-2 show the properties of steel sheets obtained under the manufacturing conditions in Tables 1-1 to 3-2. Yield strength and ultimate tensile strength were obtained by performing tensile tests. The tensile test was conducted according to JIS Z 2241:2011 by preparing a No. 5 test piece and setting the tensile axis to the rolling direction of the steel plate. The obtained yield strength (YS: Yield Strength) is 180 MPa or less, and the yield ratio (YR: Yield Ratio), which is the value obtained by dividing the yield strength by the maximum tensile strength (TS: Tensile Strength), is 0.50 or less. The steel sheet was determined to pass as having good formability. The yield strength is over 180 MPa or the yield ratio is When it was more than 0.50, it was determined to be unacceptable because the formability was poor.
[0092]
Furthermore, a test piece was obtained in the same manner as in the above tensile test, and a tensile plastic strain of 10% was applied to this test piece. After a tensile plastic strain of 10% was applied, the load was removed, the same test piece was immersed in a salt bath heated to 170° C. for 20 minutes, and then baked to cool to room temperature. After that, the same test piece was subjected to a tensile test to obtain the yield strength. Calculate the difference between the obtained yield strength and the maximum stress obtained when 10% tensile plastic strain is applied (ΔBH = yield strength after baking treatment - maximum stress when 10% tensile plastic strain is applied) did. A steel sheet having a ΔBH of 20 MPa or more was determined to be acceptable as having good bake hardenability (BH property). On the other hand, when ΔBH was less than 20 MPa, the BH properties were judged to be unacceptable.
[0093]
[Table 1-1]
[0094]
[Table 1-2]
[0095]
[Table 2-1]
[0096]
[Table 2-2]
[0097]
[Table 3-1]
[0098]
[Table 3-2]
[0099]
[Table 4-1]
[0100]
[Table 4-2]
[0101]
Of the steels A to AH shown in Tables 1-1 and 1-2, the steels AA to AH in Table 1-2 are comparative examples that deviate from the range of composition specified in the present invention.
[0102]
The AA steel had a C content higher than the range of the present invention. The steel plate of Experimental Example 65 obtained using this steel had high yield strength and high yield ratio.
[0103]
In the composition of AB steel, the value of the middle side of formula (1) was smaller than the range of the present invention. The steel plate of Experimental Example 66 obtained using this steel had a high yield ratio, and sufficient bake hardenability (BH property) was not obtained.
[0104]
In the composition of AC steel, the middle value of formula (1) was larger than the range of the present invention. In the steel plate of Experimental Example 67 obtained using this steel, unrecrystallized ferrite remained excessively, and the yield strength and yield ratio became excessively high.
[0105]
AD steel had a higher Ti content than the range of the present invention. In the steel plate of Experimental Example 68 obtained using this steel, unrecrystallized ferrite remained excessively, and the yield strength and yield ratio became excessively high.
[0106]
The AE steel had a higher Nb content than the range of the present invention. In the steel plate of Experimental Example 69 obtained using this steel, unrecrystallized ferrite remained excessively, and the yield strength and yield ratio became excessively high.
[0107]
The AF steel had a higher Si content than the range of the present invention. The steel plate of Experimental Example 70 obtained using this steel had excessively high yield strength and yield ratio.
[0108]
AG steel had a higher Mn content than the range of the present invention. The steel plate of Experimental Example 71 obtained using this steel lacked the volume fraction of ferrite and had high yield strength and high yield ratio.
[0109]
AH steel did not contain both Ti and Nb. The steel plate of Experimental Example 72 obtained using this steel had a high yield strength and a high yield ratio, and sufficient bake hardenability (BH property) was not obtained.
[0110]
Experimental Examples 7, 47, 53 and 62 are comparative examples in which the conditions of the hot rolling process deviate from the scope of the present invention.
[0111]
Experimental Examples 47 and 62 are comparative examples in which sufficient bake hardenability was not obtained because the heating temperature of the slab in the hot rolling process was low and the value of w×λ was small.
[0112]
Experimental Example 7 is a comparative example in which the rolling completion temperature in the hot rolling process was low and unrecrystallized ferrite remained in excess, resulting in excessively high yield strength and yield ratio.
[0113]
Experimental Example 53 is a comparative example in which sufficient bake hardenability was not obtained because the average cooling rate in the temperature range from the hot rolling completion temperature to 500° C. in the hot rolling step was small and the value of w×λ was small. is.
[0114]
Experimental Examples 16, 29, 58 and 64 are comparative examples in which the conditions of the reheating process deviate from the scope of the present invention.
[0115]
Experimental example 29 is a comparative example in which the maximum reheating temperature in the reheating process was high and the value of w x λ was small, resulting in an excessively high yield ratio and insufficient bake hardenability.
[0116]
Experimental example 58 is a comparative example in which the maximum reheating temperature in the reheating process was low and the value of w x λ was small, resulting in a high yield ratio and insufficient bake hardenability.
[0117]
Experimental Examples 16 and 64 are comparative examples in which the temperature history in the reheating step did not satisfy the formula (3) (K20 was low) and the value of w×λ was small, so sufficient bake hardenability was not obtained. is.
[0118]
Experimental Examples 6, 15 and 28 are comparative examples in which the conditions of the cold rolling process deviate from the scope of the present invention.
[0119]
Experimental Example 6 is a comparative example in which the yield strength and yield ratio were increased due to the high total rolling reduction in the cold rolling process and the excessive residual non-recrystallized ferrite.
[0120]
Experimental Example 15 is a comparative example in which the yield strength and yield ratio are high because the total rolling reduction in the cold rolling process is low and unrecrystallized ferrite remains excessively.
[0121]
Experimental Example 28 is a comparative example in which the yield strength and yield ratio were increased because the rolling completion temperature in the cold rolling process was high and unrecrystallized ferrite remained excessively.
[0122]
Experimental Examples 2, 27, 33, 40, 46, 51, 56 and 61 are comparative examples in which the conditions of the annealing process are outside the scope of the present invention.
[0123]
Experimental example 61 is a comparative example in which sufficient bake hardenability was not obtained because the annealing temperature in the holding process of the annealing step was high and the value of w x λ was small.
[0124]
In Experimental Example 46, the annealing temperature in the holding process of the annealing step was low, unrecrystallized ferrite remained excessively, and the value of w × λ became small. This is a comparative example in which curability was not obtained.
[0125]
Experimental example 56 is a comparative example in which sufficient bake hardenability was not obtained because the temperature history in the heating process of the annealing step did not satisfy the expression (4) and the value of w×λ was small.
[0126]
In Experimental Example 2, the temperature history in the heating process of the annealing step did not satisfy the expression (4), unrecrystallized ferrite remained excessively, and the value of w × λ became small, so the yield strength and yield ratio were high. This is a comparative example in which sufficient bake hardenability was not obtained.
[0127]
Experimental Example 33 is a comparative example in which the temperature history in the cooling process of the annealing step did not satisfy the expression (5), the value of w×λ was small, the yield ratio was high, and sufficient bake hardenability was not obtained. be.
[0128]
Experimental example 51 is a comparative example in which the temperature history in the cooling process of the annealing process did not satisfy the expression (5), and structures other than ferrite were excessively formed, resulting in high yield strength and yield ratio.
[0129]
In Experimental Example 27, bending was not performed in the temperature range of 80 to 500°C in the cooling process of the annealing process, and the value of w × λ became small, so the yield ratio increased and sufficient bake hardenability was obtained. This is a comparative example that was not possible.
[0130]
In Experimental Example 40, in the cooling process of the annealing process, bending was performed without applying sufficient tension in the temperature range of 80 to 500 ° C., and the value of w × λ became small, so sufficient bake hardenability was obtained. This is a comparative example that was not possible.
[0131]
Experimental Examples 11 and 43 are comparative examples in which the conditions of the temper rolling process deviate from the scope of the present invention.
[0132]
In Experimental Example 43, the total rolling reduction of the temper rolling in the temper rolling step was large, unrecrystallized ferrite remained excessively, and the value of w × λ became small, so that the yield strength and the yield ratio increased. Also, this is a comparative example in which sufficient bake hardenability was not obtained.
[0133]
Experimental example 11 is a comparative example in which sufficient bake hardenability was not obtained because the total rolling reduction of the temper rolling in the temper rolling process was small and the value of w×λ was small.
[0134]
Experimental examples excluding the above comparative examples are examples of the present invention. It can be seen that the steel sheets described as examples can have a reduced yield strength and high bake hardenability in a high strain region by being manufactured by a manufacturing method that satisfies the manufacturing conditions of the present invention.
[0135]
Experimental Examples 4, 5, 8, 9, 12, 18, 21, 24, 26, 31, 35, 37, 38, 41, 45, 48, 50, 52, 55, 57, 60 and 63 were subjected to plating treatment. It is an example in which a plated steel sheet of the present invention was obtained by applying.
[0136]
In Experimental Examples 8, 21, 24, 41, 45 and 50, the steel sheets were cooled to 500°C in the annealing process, then immersed in a molten zinc bath and cooled to room temperature to obtain hot-dip galvanized steel sheets (GI). It is an example.
[0137]
Experimental Examples 5, 18, 26, 35, 37, 48, 52, 55, 57 and 60 are alloying treatments in which the steel sheet is cooled to 500°C in the annealing step, immersed in a molten zinc bath, and then reheated to 560°C. It is an example in which an alloyed hot-dip galvanized steel sheet (GA) was obtained by cooling to room temperature after applying.
[0138]
Experimental Examples 4 and 38 are examples in which a steel sheet was cooled to 500°C in the annealing process, then immersed in a molten zinc alloy bath, and cooled to room temperature to obtain a zinc alloy plated steel sheet.
[0139]
In Experimental Example 9, the steel sheet was cooled to 500°C in the annealing process, immersed in a molten zinc alloy bath, subjected to alloying treatment by reheating to 580°C, and then cooled to room temperature to obtain an alloyed zinc alloy. It is an example in which a plated steel sheet was obtained.
[0140]
Experimental example 12 is an example in which a galvanized steel sheet was obtained by performing vapor deposition plating after temper rolling.
[0141]
Experimental Examples 31 and 63 are examples in which an electrogalvanized steel sheet (EG) was obtained by performing an electrogalvanizing treatment after the annealing process.
Industrial applicability
[0142]
As described above, according to the present invention, it is possible to provide a steel sheet with excellent formability and BH properties. Since the steel sheet of the present invention is a steel sheet suitable for significantly reducing the weight of automobiles and ensuring the protection and safety of passengers, the present invention has high applicability in the steel sheet manufacturing industry and the automobile industry.
The scope of the claims
[Claim 1]
The component composition is mass %,
C: 0.0003 to 0.0100%,
Si: 0.005 to 1.500%,
Mn: 0.010 to 3.000%,
Al: 0.005 to 1.000%,
P: 0.100% or less,
S: 0.0200% or less,
N: 0.0150% or less,
O: 0.0100% or less,
V: 0 to 0.50%,
Cr: 0 to 1.00%,
Ni: 0 to 1.00%,
Cu: 0 to 1.00%,
Mo: 0 to 1.00%,
W: 0 to 1.00%,
B: 0 to 0.0100%,
Sn: 0 to 1.00%,
Sb: 0-0.20%, and
one or more of Ca, Ce, Mg, Zr, La and REM: 0 to 0.0100%,
contains
Ti: 0.010 to 0.100%, and
Nb: 0.005 to 0.060% containing one or two types,
satisfies the following formula (1),
The balance consists of Fe and impurities,
The microstructure at the 1/4 position of the plate thickness in the plate thickness direction from the surface is
By volume %, ferrite: 95% or more, residual structure: 5% or less,
The ratio of non-recrystallized ferrite in the ferrite is 5% or less,
The half width w and the X-ray wavelength λ at the peak of the (200) plane of the ferrite satisfy the following formula (2)
A steel plate characterized by:
0.80≦{(Ti/48−N/14)+Nb/93}/(C/12)≦5.00 (1)
w×λ≧0.20 (2)
Ti, N, Nb and C in the above formula (1) indicate the content in mass% of each element, and 0 is substituted when the element is not contained.
[Claim 2]
The above component composition is in mass %,
V: 0.01 to 0.50%,
Cr: 0.05 to 1.00%,
Ni: 0.05 to 1.00%,
Cu: 0.05 to 1.00%,
Mo: 0.03 to 1.00%,
W: 0.03 to 1.00%,
B: 0.0005 to 0.0100%,
Sn: 0.01 to 1.00%,
Sb: 0.005-0.20%, and
One or more of Ca, Ce, Mg, Zr, La and REM: 0.0001 to 0.0100%
The steel sheet according to claim 1, characterized by containing one or more selected from the group consisting of:
[Claim 3]
The steel sheet according to claim 1 or claim 2, wherein the ferrite contained in the microstructure has an average grain size of 6.0 to 15.0 µm.
[Claim 4]
The steel sheet according to any one of claims 1 to 3, characterized by having a galvanized layer on the surface.
[Claim 5]
The steel sheet according to any one of claims 1 to 3, characterized by having a zinc alloy plating layer on the surface.
[Claim 6]
The steel sheet according to claim 4 or 5, wherein the Fe content in the zinc plating layer or the zinc alloy plating layer is 7.0 to 13.0% by mass.
[Claim 7]
A method for manufacturing the steel sheet according to any one of claims 1 to 3,
A steel slab having the chemical composition according to claim 1 is heated to 1200 to 1320 ° C., hot rolling is completed so that the hot rolling completion temperature is 880 ° C. or higher, and the hot rolling completion temperature to 500 ° C. A hot rolling step of cooling to a hot-rolled steel sheet by cooling so that the average cooling rate in the temperature range is 20 ° C./s or more;
a reheating step of heating the hot-rolled steel sheet to a temperature range of 500 to 700°C;
a cooling step of cooling the hot-rolled steel sheet to room temperature;
A cold-rolling step of cold-rolling the hot-rolled steel sheet so that the total rolling reduction is 60 to 90% and the cold-rolling completion temperature is 250°C or less to obtain a cold-rolled steel sheet;
An annealing step of heating the cold-rolled steel sheet to an annealing temperature of 700 to 850°C and cooling it to a temperature range of 80°C or less;
and a temper rolling step of temper rolling the cold-rolled steel sheet so that the total rolling reduction is 0.05 to 2.00%,
In the reheating process,
In the temperature range of 500 to 700°C, the following formula (3) is satisfied,
In the annealing process,
In the heating process to the annealing temperature,
In the temperature range from 700°C to the annealing temperature, the following formula (4) is satisfied,
In the cooling process from the annealing temperature,
In the temperature range of 500 to 700°C, the following formula (5) is satisfied,
In a temperature range of 80 to 500°C, bending is performed while applying a tension of 20 MPa or more
A steel plate manufacturing method characterized by:
[Number 1]
In the above formula (3), K 20 is the carbonitriding of Ti and / or Nb in the 20th section when the temperature history in the temperature range of 500 to 700 ° C. in the reheating process is equally divided into 20 times. It is an index showing the degree of progress of deposition of substances. t n and K n are calculated by dividing the temperature history in the temperature range of 500 to 700 ° C in the reheating process by 20 equally with respect to time, and taking the average temperature in the n-th interval as T n [° C]. is. Δt K is the time [hr. ] represents. C, Nb and Ti represent the content [% by mass] of each element. However, t1=ΔtK.
[Number 2]
In the above formula (4), R i is the degree of progress of recrystallization in the temperature range from 700 ° C. to the annealing temperature, and the amount of C from Ti and / or Nb carbonitrides present at the grain boundaries to the grains. It is an index that indicates the progress of diffusion. R m is obtained by dividing the temperature history of the steel sheet from 700 ° C. to the annealing temperature in the heating process of the annealing process into 10 equal parts with respect to time, and taking the average temperature in the m-th section as T m [° C.]. It is calculated. Δt R represents the time [seconds] obtained by dividing the total residence time in the temperature range from 700° C. to the annealing temperature by 10. K20 is the value obtained by the above equation (3). A and B are constant terms, A is 9.67×10 9 and B is 1.25×10 4 .
[Number 3]
In the above formula (5), Pj is an index that indicates the progress of precipitation of C in the temperature range of 700 to 500°C. In the cooling process of the annealing process, P k divides the temperature history of the steel sheet from reaching 700 ° C. to reaching 500 ° C. into 10 times, and the average temperature in the k-th section is T It is calculated as k [°C]. Δt P represents the time [seconds] obtained by dividing the total staying time in the same temperature range by 10. R10 is a value obtained by substituting 10 for m of Rm in formula (4). D, E and F are constant terms, D is 4.47×10 4 , E is 2.11×10 0 and F is 1.25×10 4 .
[Claim 8]
The steel sheet manufacturing method according to claim 7, wherein the cold-rolled steel sheet is subjected to a hot-dip galvanizing treatment in the cooling process of the annealing process.
[Claim 9]
The steel sheet manufacturing method according to claim 7, wherein the cold-rolled steel sheet is subjected to a hot-dip zinc alloy plating treatment in the cooling process of the annealing process.
[Claim 10]
10. The method for manufacturing the steel sheet according to claim 8 or 9, characterized in that in the cooling process of the annealing step, alloying treatment is performed after the hot dip galvanizing treatment or after the hot dip galvanizing treatment.
| Section | Controller | Decision Date |
|---|---|---|
| # | Name | Date |
|---|---|---|
| 1 | 202217035210-IntimationOfGrant11-03-2024.pdf | 2024-03-11 |
| 1 | 202217035210.pdf | 2022-06-20 |
| 2 | 202217035210-PatentCertificate11-03-2024.pdf | 2024-03-11 |
| 2 | 202217035210-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [20-06-2022(online)].pdf | 2022-06-20 |
| 3 | 202217035210-STATEMENT OF UNDERTAKING (FORM 3) [20-06-2022(online)].pdf | 2022-06-20 |
| 3 | 202217035210-ABSTRACT [01-05-2023(online)].pdf | 2023-05-01 |
| 4 | 202217035210-REQUEST FOR EXAMINATION (FORM-18) [20-06-2022(online)].pdf | 2022-06-20 |
| 4 | 202217035210-AMMENDED DOCUMENTS [01-05-2023(online)].pdf | 2023-05-01 |
| 5 | 202217035210-PROOF OF RIGHT [20-06-2022(online)].pdf | 2022-06-20 |
| 5 | 202217035210-CLAIMS [01-05-2023(online)].pdf | 2023-05-01 |
| 6 | 202217035210-PRIORITY DOCUMENTS [20-06-2022(online)].pdf | 2022-06-20 |
| 6 | 202217035210-COMPLETE SPECIFICATION [01-05-2023(online)].pdf | 2023-05-01 |
| 7 | 202217035210-POWER OF AUTHORITY [20-06-2022(online)].pdf | 2022-06-20 |
| 7 | 202217035210-FER_SER_REPLY [01-05-2023(online)].pdf | 2023-05-01 |
| 8 | 202217035210-FORM 18 [20-06-2022(online)].pdf | 2022-06-20 |
| 8 | 202217035210-FORM 13 [01-05-2023(online)].pdf | 2023-05-01 |
| 9 | 202217035210-FORM 1 [20-06-2022(online)].pdf | 2022-06-20 |
| 9 | 202217035210-MARKED COPIES OF AMENDEMENTS [01-05-2023(online)].pdf | 2023-05-01 |
| 10 | 202217035210-DECLARATION OF INVENTORSHIP (FORM 5) [20-06-2022(online)].pdf | 2022-06-20 |
| 10 | 202217035210-OTHERS [01-05-2023(online)].pdf | 2023-05-01 |
| 11 | 202217035210-COMPLETE SPECIFICATION [20-06-2022(online)].pdf | 2022-06-20 |
| 11 | 202217035210-FER.pdf | 2022-11-15 |
| 12 | 202217035210-FORM 3 [09-11-2022(online)].pdf | 2022-11-09 |
| 12 | 202217035210-Verified English translation [20-07-2022(online)].pdf | 2022-07-20 |
| 13 | 202217035210-FORM 3 [09-11-2022(online)].pdf | 2022-11-09 |
| 13 | 202217035210-Verified English translation [20-07-2022(online)].pdf | 2022-07-20 |
| 14 | 202217035210-COMPLETE SPECIFICATION [20-06-2022(online)].pdf | 2022-06-20 |
| 14 | 202217035210-FER.pdf | 2022-11-15 |
| 15 | 202217035210-DECLARATION OF INVENTORSHIP (FORM 5) [20-06-2022(online)].pdf | 2022-06-20 |
| 15 | 202217035210-OTHERS [01-05-2023(online)].pdf | 2023-05-01 |
| 16 | 202217035210-FORM 1 [20-06-2022(online)].pdf | 2022-06-20 |
| 16 | 202217035210-MARKED COPIES OF AMENDEMENTS [01-05-2023(online)].pdf | 2023-05-01 |
| 17 | 202217035210-FORM 18 [20-06-2022(online)].pdf | 2022-06-20 |
| 17 | 202217035210-FORM 13 [01-05-2023(online)].pdf | 2023-05-01 |
| 18 | 202217035210-POWER OF AUTHORITY [20-06-2022(online)].pdf | 2022-06-20 |
| 18 | 202217035210-FER_SER_REPLY [01-05-2023(online)].pdf | 2023-05-01 |
| 19 | 202217035210-PRIORITY DOCUMENTS [20-06-2022(online)].pdf | 2022-06-20 |
| 19 | 202217035210-COMPLETE SPECIFICATION [01-05-2023(online)].pdf | 2023-05-01 |
| 20 | 202217035210-PROOF OF RIGHT [20-06-2022(online)].pdf | 2022-06-20 |
| 20 | 202217035210-CLAIMS [01-05-2023(online)].pdf | 2023-05-01 |
| 21 | 202217035210-REQUEST FOR EXAMINATION (FORM-18) [20-06-2022(online)].pdf | 2022-06-20 |
| 21 | 202217035210-AMMENDED DOCUMENTS [01-05-2023(online)].pdf | 2023-05-01 |
| 22 | 202217035210-STATEMENT OF UNDERTAKING (FORM 3) [20-06-2022(online)].pdf | 2022-06-20 |
| 22 | 202217035210-ABSTRACT [01-05-2023(online)].pdf | 2023-05-01 |
| 23 | 202217035210-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [20-06-2022(online)].pdf | 2022-06-20 |
| 23 | 202217035210-PatentCertificate11-03-2024.pdf | 2024-03-11 |
| 24 | 202217035210.pdf | 2022-06-20 |
| 24 | 202217035210-IntimationOfGrant11-03-2024.pdf | 2024-03-11 |
| 1 | searchE_11-11-2022.pdf |