Abstract: The non-oriented electromagnetic steel sheet according to one embodiment of the present invention has a chemical composition containing 0.0030% or less of C, 2.00% or less of Si, 1.00% or less of Al, 0.10-2.00% of Mn, 0.0030% or less of S, a total of more than 0.0100% but not more than 0.0250% of one or more selected from the group consisting of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn, and Cd, parameter Q represented by Q = [Si] + 2 × [Al] - [Mn] being 2.00 or less, 0.00-0.40% of Sn, and 0.00-1.00% of Cu. The remaining portion is Fe and impurities, and parameter R is represented by R = (I100 + I310 + I411 + I521)/(I111 + I211 + I332 + I221) being 0.80 or more.
Specification
Title of invention: Non-oriented electrical steel sheet and method for manufacturing non-oriented electrical steel sheet
Technical field
[0001]
The present invention relates to non-oriented electrical steel sheets and a method for manufacturing non-oriented electrical steel sheets.
The present application claims priority based on Japanese Patent Application No. 2018-026098 filed in Japan on February 16, 2018, the contents of which are incorporated herein by reference.
Background technology
[0002]
The non-oriented electrical steel sheet is used, for example, in the iron core of a motor, and the non-oriented electrical steel sheet is required to have excellent magnetic characteristics, for example, a high magnetic flux density. So far, various techniques such as those disclosed in Patent Documents 1 to 9 have been proposed, but it is difficult to obtain a sufficient magnetic flux density.
Prior art literature
Patent documents
[0003]
Patent Document 1: Japanese Patent Application Laid-Open No. 2-133523
Patent Document 2: Japanese Patent Application Laid-Open No. 5-140648
Patent Document 3: Japanese Patent Application Laid-Open No. 6-0573332
Patent Document 4: Japanese Patent Application Laid-Open No. 2002-241905 JP
Patent Document 5: Japanese Patent 2004-197217 JP
Patent Document 6: Japanese Patent 2004-332042 JP
Patent Document 7: Japanese Patent 2005-067737 JP
Patent Document 8: Japanese Patent 2011 -140683
Patent Document 9: Japanese Patent Application Laid-Open No. 2010-1557
Outline of the invention
Problems to be solved by the invention
[0004]
An object of the present invention is to provide a non-oriented electrical steel sheet capable of obtaining a higher magnetic flux density without deteriorating iron loss, and a method for manufacturing the non-oriented electrical steel sheet.
Means to solve problems
[0005]
The present inventors have conducted diligent studies to solve the above problems. As a result, it became clear that it is important to make the relationship between the chemical composition and the crystal orientation appropriate. It was also clarified that this relationship should be maintained throughout the thickness direction of non-oriented electrical steel sheets. The isotropic texture of the texture of the rolled steel sheet is high in the region close to the rolled surface and usually decreases as the distance from the rolled surface increases. For example, in the invention described in Patent Document 9, it is shown in the experimental data disclosed in the same document that the isotropic property of the texture decreases as the measurement position of the texture decreases from the surface layer. The present inventors have found that it is necessary to preferably control the crystal orientation even inside the non-oriented electrical steel sheet.
In Patent Document 9, the crystal orientations are accumulated near the cube orientation near the surface layer of the steel sheet, whereas the gamma fiber texture is developed in the central layer of the steel sheet. Patent Document 9 explains that a novel feature is that the texture is significantly different between the surface layer of the steel sheet and the center layer of the steel sheet. In general, when a rolled steel sheet is annealed and recrystallized, crystal orientations are accumulated near the cube orientations {200} and {110} near the surface layer of the steel sheet, and a gamma fiber texture is formed in the central layer of the steel sheet. A {222} develops. For example, "Effect of cold rolling conditions on r value of ultra-low carbon cold rolled steel sheet", Hashimoto et al., Iron and Steel, Vol. 76, No. 1 (1990), P.M. At 50, 0.0035% C-0.12% Mn-0.001% P-0.0084% S-0.03% Al-0.11% Ti steel was cold-rolled at a reduction rate of 73%. In the steel sheet obtained by annealing at 750 ° C. for 3 hours, it is shown that the center of the thickness is higher at (222), lower at (200), and lower at (110) than the surface layer.
On the other hand, the present inventors need to accumulate the crystal orientation near {200}, which is the cube orientation, near the surface layer of the steel sheet, and also to accumulate the crystal orientation near {200} in the central layer of the steel sheet. I found out.
[0006]
In the production of such non-oriented electrical steel sheets, when obtaining steel strips to be subjected to cold rolling such as hot-rolled steel strips, the columnar crystal ratio and average grain grain size in casting or rapid solidification of molten steel are controlled. It was also clarified that it is important to control the rolling reduction of cold rolling and to control the sheet tension and cooling rate during finish annealing.
[0007]
As a result of further diligent studies based on such findings, the present inventors have come up with various aspects of the invention shown below.
[0008]
(1) The non-directional electromagnetic steel plate according to one aspect of the present invention has a mass% of C: 0.0030% or less, Si: 2.00% or less, Al: 1.00% or less, Mn: 0.10. % To 2.00%, S: 0.0030% or less, one or more selected from the group consisting of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn and Cd: 0.0100% in total The formula 1 is expressed by defining the Si content (mass%) as [Si], the Al content (mass%) as [Al], and the Mn content (mass%) as [Mn]. It has a chemical composition represented by the parameters Q: 2.00 or less, Sn: 0.00% to 0.40%, Cu: 0.00% to 1.00%, and the balance: Fe and impurities. , {100} Crystal Orientation Strength at the Center of Plate Thickness, {310} Crystal Orientation Strength, {411} Crystal Orientation Strength, {521} Crystal Orientation Strength, {111} Crystal Orientation Strength, {211} Crystal Orientation Strength, {332 } Crystal orientation strength and {221} Crystal orientation strength are defined as I 100 , I 310 , I 411 , I 521 , I 111 , I 211 , I 332 , and I 221 respectively, and the parameter R represented by Equation 2 is 0. .80 or more.
Q = [Si] + 2 × [Al]-[Mn] (Equation 1)
R = (I 100 + I) 310 + I 411 + I 521 ) / (I 111 + I 211 + I 332 + I 221 ) (Equation 2)
(2) In the non-oriented electrical steel sheet according to (1) above, Sn: 0.02% to 0.40%, Cu: 0.10% to 1.00%, or both may be satisfied.
(3) The method for producing a non-directional electromagnetic steel sheet according to another aspect of the present invention is the method for producing a non-directional electromagnetic steel sheet according to the above (1) or (2), which is a continuous casting step of molten steel. , The hot rolling step of the ingot obtained by the continuous casting step, the cold rolling step of the steel strip obtained by the hot rolling step, and the finishing of the cold rolled steel sheet obtained by the cold rolling step. The molten steel has the chemical composition described in (1) or (2) above, and the steel strip has a columnar crystal ratio of 80% or more in terms of area fraction and an average crystal. The particle size is 0.10 mm or more, and the rolling reduction in the cold rolling step is 90% or less.
(4) In the method for manufacturing non-oriented electrical steel sheets according to (3) above, even if the temperature difference between one surface and the other surface of the steel ingot during solidification in the continuous casting step is 40 ° C. or more. Good.
(5) In the method for manufacturing non-oriented electrical steel sheets according to (3) or (4) above, in the hot rolling step, the start temperature of hot rolling is set to 900 ° C. or lower, and the steel strip is wound. The temperature may be 650 ° C. or lower.
(6) In the method for manufacturing grain-oriented electrical steel sheet according to any one of (3) to (5) above, the sheet tension in the finish annealing step is set to 3 MPa or less, and the cooling rate at 950 ° C to 700 ° C. May be 1 ° C./sec or less.
(7) The method for producing a non-directional electromagnetic steel sheet according to another aspect of the present invention is the method for producing a non-directional electromagnetic steel sheet according to the above (1) or (2), which is the same as the rapid solidification step of molten steel. The molten steel includes the cold rolling step of the steel strip obtained by the rapid solidification step and the finish annealing step of the cold rolled steel sheet obtained by the cold rolling step, and the molten steel is the above (1) or (2). ), The steel strip has a columnar crystal ratio of 80% or more in terms of area fraction and an average crystal grain size of 0.10 mm or more, and the rolling reduction in the cold rolling step. Is 90% or less.
(8) In the method for producing a non-oriented electrical steel sheet according to (7) above, in the rapid solidification step, the molten steel is solidified by using a moving and renewing cooling body and injected into the moving and renewing cooling body. The temperature of the molten steel may be 25 ° C. or higher higher than the solidification temperature of the molten steel.
(9) In the method for producing a non-oriented electrical steel sheet according to (7) or (8) above, in the rapid solidification step, the molten steel is solidified using a moving and renewing cooling body, and the solidification of the molten steel is completed. The average cooling rate until winding of the steel strip may be 1,000 to 3,000 ° C./min.
(10) In the method for manufacturing grain-oriented electrical steel sheet according to any one of (7) to (9) above, the sheet tension in the finish annealing step is set to 3 MPa or less, and the cooling rate at 950 ° C to 700 ° C. May be 1 ° C./sec or less.
Effect of the invention
[0009]
According to the present invention, since the relationship between the chemical composition and the crystal orientation is appropriate, a high magnetic flux density can be obtained without deteriorating the iron loss.
Mode for carrying out the invention
[0010]
Hereinafter, embodiments of the present invention will be described in detail.
[0011]
First, the chemical composition of the non-oriented electrical steel sheet according to the embodiment of the present invention and the molten steel used for manufacturing the same will be described. Although details will be described later, the non-oriented electrical steel sheet according to the embodiment of the present invention is manufactured through casting and hot rolling of molten steel, rapid solidification of molten steel, cold rolling, finish annealing and the like. Therefore, the chemical composition of the non-oriented electrical steel sheet and the molten steel takes into consideration not only the characteristics of the non-oriented electrical steel sheet but also these treatments. In the following description, "%", which is a unit of the content of each element contained in non-oriented electrical steel sheets or molten steel, means "mass%" unless otherwise specified. The non-oriented electrical steel sheet according to this embodiment has C: 0.0030% or less, Si: 2.00% or less, Al: 1.00% or less, Mn: 0.10% to 2.00%, S: 0.0030% or less, one or more selected from the group consisting of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn and Cd: more than 0.0100% and less than 0.0250% in total, containing Si Parameter Q: 2.00 or less represented by Equation 1 with the amount (% by mass) defined as [Si], the Al content (% by mass) as [Al], and the Mn content (% by mass) as [Mn]. , Sn: 0.00% to 0.40%, Cu: 0.00% to 1.00%, and the balance: Fe and a chemical composition represented by impurities. Examples of impurities include those contained in raw materials such as ore and scrap, and those contained in the manufacturing process.
Q = [Si] + 2 × [Al]-[Mn] (Equation 1)
[0012]
(C: 0.0030% or less)
C increases iron loss and causes magnetic aging. Therefore, the lower the C content, the better, and it is not necessary to set the lower limit. The lower limit of the C content may be 0%, 0.0001%, 0.0002%, 0.0005%, or 0.0010%. Such a phenomenon is remarkable when the C content exceeds 0.0030%. Therefore, the C content is set to 0.0030% or less. The upper limit of the C content may be 0.0028%, 0.0025%, 0.0022%, or 0.0020%.
[0013]
(Si: 0.30% or more, 2.00% or less) As
is well known, Si is a component having an action of reducing iron loss, and is contained in order to exert this action. If the Si content is less than 0.30%, the iron loss reduction effect is not sufficiently exhibited, so the lower limit of the Si content is set to 0.30%. For example, the lower limit of the Si content may be 0.90%, 0.95%, 0.98%, or 1.00%. On the other hand, when the Si content increases, the magnetic flux density decreases, the rolling workability deteriorates, and the cost increases, so the value is set to 2.0% or less. The upper limit of the Si content may be 1.80%, 1.60%, 1.40%, or 1.10%.
[0014]
(Al: 1.00% or less)
Al has the effect of increasing electrical resistance and reducing iron loss, similar to Si. Further, when the non-oriented electrical steel sheet contains Al, the texture obtained by primary recrystallization may be a crystal whose plane parallel to the plate surface is {100} plane (hereinafter, “{100} crystal””. ) Is likely to be developed. Al is contained in order to exert this action. For example, the lower limit of the Al content may be 0%, 0.01%, 0.02%, or 0.03%. On the other hand, if the Al content exceeds 1.00%, the magnetic flux density decreases as in the case of Si, so the content is set to 1.00% or less. The upper limit of the Al content may be 0.50%, 0.20%, 0.10%, or 0.05%.
[0015]
(Mn: 0.10% to 2.00%)
Mn increases the electric resistance, reduces the eddy current loss, and reduces the iron loss. When Mn is contained, the texture obtained by primary recrystallization tends to be a crystal in which a plane parallel to the plate surface is {100}. The {100} crystal is a crystal suitable for uniformly improving the magnetic properties in all directions in the plate surface. Further, the higher the Mn content, the higher the precipitation temperature of MnS, and the larger the amount of MnS precipitated. Therefore, the higher the Mn content, the less likely it is that fine MnS having a particle size of about 100 nm, which inhibits recrystallization and growth of crystal grains in finish annealing, is precipitated. If the Mn content is less than 0.10%, these effects cannot be sufficiently obtained. Therefore, the Mn content is set to 0.10% or more. The lower limit of the Mn content may be 0.12%, 0.15%, 0.18%, or 0.20%. On the other hand, when the Mn content exceeds 2.00%, the crystal grains do not grow sufficiently in the finish annealing, and the iron loss increases. Therefore, the Mn content is set to 2.00% or less. The upper limit of the Mn content may be 1.00%, 0.50%, 0.30%, or 0.25%.
[0016]
(S: 0.0030% or less)
S is not an essential element and is contained as an impurity in steel, for example. S inhibits recrystallization and grain growth in finish annealing due to the precipitation of fine MnS. Therefore, the lower the S content, the better. Such an increase in iron loss is remarkable when the S content exceeds 0.0030%. Therefore, the S content is set to 0.0030% or less. The lower limit of the S content does not need to be specified, and may be, for example, 0%, 0.0005%, 0.0010%, or 0.0015%.
[0017]
(One or more selected from the group consisting of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn and Cd: more than 0.0100% and 0.0250% or less in total)
Mg, Ca, Sr, Ba , Nd, Pr, La, Ce, Zn and Cd react with S in the molten steel during casting or rapid solidification of the molten steel to produce sulfides, acid sulfides or both precipitates. Hereinafter, Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn and Cd may be collectively referred to as "coarse precipitate-forming element". The particle size of the precipitate of the coarse precipitate-forming element is about 1 μm to 2 μm, which is much larger than the particle size of fine precipitates such as MnS, TiN, and AlN (about 100 nm). Therefore, these fine precipitates adhere to the precipitates of coarse precipitate-forming elements, and it becomes difficult to inhibit recrystallization and growth of crystal grains in finish annealing. If the total content of the coarse precipitate-forming elements is 0.0100% or less, these effects cannot be sufficiently obtained. Therefore, the total content of the coarse precipitate-forming element is more than 0.0100%. The lower limit of the content of the coarse precipitate-forming element may be 0.0110%, 0.0120%, 0.0150%, or 0.0170% in total. On the other hand, when the total content of coarse precipitate-forming elements exceeds 0.0250%, precipitates other than sulfides or acid sulfides are likely to be generated, and rather, recrystallization and grain growth in finish annealing are inhibited. The Rukoto. Therefore, the total content of the coarse precipitate-forming element is 0.0250% or less. The upper limit of the content of the coarse precipitate-forming element may be 0.0240%, 0.0230%, 0.0220%, or 0.0210% in total.
According to the experimental results of the present inventors, as long as the content of the coarse precipitate-forming element is within the above range, the effect of the coarse precipitate is surely exhibited, and the crystal grains of the non-oriented electrical steel sheet are sufficient. Was growing up. Therefore, it is not necessary to particularly limit the morphology and components of the coarse precipitate produced by the coarse precipitate-forming element. On the other hand, in the non-oriented electrical steel sheet according to the present embodiment, the total mass of S contained in the sulfide or acid sulfide of the coarse precipitate-forming element is 40% of the total mass of S contained in the non-oriented electrical steel sheet. The above is preferable. As described above, the coarse precipitate-forming element reacts with S in the molten steel during casting or rapid solidification of the molten steel to form sulfides, acid sulfides, or both precipitates. Therefore, a high ratio of the total mass of S contained in the sulfide or acid sulfide of the coarse precipitate-forming element to the total mass of S contained in the non-directional electromagnetic steel plate is a sufficient amount of coarse precipitate formation. It means that the element is contained in the non-directional electromagnetic steel plate, and fine precipitates such as MnS are effectively attached to the precipitates. Therefore, the higher the ratio, the more the recrystallization and the growth of crystal grains in the finish annealing are promoted, and excellent magnetic properties can be obtained. The above ratio is achieved, for example, by controlling the production conditions at the time of casting or rapid solidification of molten steel as described later.
[0018]
(Parameter Q: 2.00 or less)
Parameter Q defines Si content (mass%) as [Si], Al content (mass%) as [Al], and Mn content (mass%) as [Mn]. It is a value expressed by Equation 1.
Q = [Si] + 2 × [Al]-[Mn] (Equation 1) By
setting the parameter Q to 2.00 or less, the transformation from austenite to ferrite during cooling after continuous casting or rapid solidification of molten steel (formulation of austenite to ferrite ( γ → α transformation) is likely to occur, and the {100} <0vw> texture of columnar crystals is sharpened. The upper limit of the parameter Q may be 1.50%, 1.20%, 1.00%, 0.90%, or 0.88%. The lower limit of the parameter Q is not particularly limited, but may be, for example, 0.20%, 0.40%, 0.80%, 0.82%, or 0.85%.
[0019]
Sn and Cu are not essential elements, and the lower limit of their content is 0%, but they are optional elements that may be appropriately contained in the non-oriented electrical steel sheet up to a predetermined amount.
[0020]
(Sn: 0.00% to 0.40%, Cu: 0.00% to 1.00%)
Sn and Cu develop crystals suitable for improving magnetic properties by primary recrystallization. Therefore, when Sn, Cu, or both of them are contained, a texture in which {100} crystals suitable for uniformly improving the magnetic properties in all directions in the plate surface are developed can be easily obtained by primary recrystallization. Sn suppresses oxidation and nitriding of the surface of the steel sheet during finish annealing, and suppresses variation in crystal grain size. Therefore, Sn, Cu, or both may be contained. In order to sufficiently obtain these effects, Sn: 0.02% or more, Cu: 0.10% or more, or both of them are preferable. The lower limit of the Sn content may be 0.05%, 0.08%, or 0.10%. The lower limit of the Cu content may be 0.12%, 0.15%, or 0.20%. On the other hand, when Sn exceeds 0.40%, the above-mentioned effects are saturated and the cost is unnecessarily high, or the growth of crystal grains is suppressed in finish annealing. Therefore, the Sn content is set to 0.40% or less. The upper limit of the Sn content may be 0.35%, 0.30%, or 0.20%. If the Cu content exceeds 1.00%, the steel sheet becomes brittle, making hot rolling and cold rolling difficult, and finishing annealing of the annealing line becomes difficult. Therefore, the Cu content is set to 1.00% or less. The upper limit of the Cu content may be 0.80%, 0.60%, or 0.40%.
[0021]
Next, the texture of the non-oriented electrical steel sheet according to the embodiment of the present invention will be described. In the non-directional electromagnetic steel plate according to the present embodiment, {100} crystal orientation strength, {310} crystal orientation strength, {411} crystal orientation strength, {521} crystal orientation strength, {111} crystal orientation at the center of the plate thickness. The strength, {211} crystal orientation strength, {332} crystal orientation strength, and {221} crystal orientation strength are defined as I 100 , I 310 , I 411 , I 521 , I 111 , I 211 , I 332 , and I 221 respectively. , The parameter R represented by the equation 2 is 0.80 or more. The central portion of the plate thickness (usually referred to as 1 / 2T portion) is a depth of about 1/2 of the plate thickness T of the non-oriented electrical steel sheet from the rolled surface of the non-oriented electrical steel sheet. It means the area of rolling steel. In other words, the central portion of the sheet thickness means the intermediate surface between the rolled surfaces of the non-oriented electrical steel sheet and its vicinity.
R = (I 100 + I 310 + I 411 + I 521 ) / (I 111 + I 211 + I 332 + I 221 ) (Equation 2)
[0022]
{310}, {411} and {521} are in the vicinity of {100}, and the sum of I 100 , I 310 , I 411 and I 521 is the crystal orientation in the vicinity of {100}, including {100} itself. Shows the sum of intensities. {211}, {332} and {221} are in the vicinity of {111}, and the sum of I 111 , I 211 , I 332 and I 221 is in the crystal orientation near {111}, including {111} itself. Shows the sum of intensities. If the parameter R at the center of the plate thickness is less than 0.80, the magnetic characteristics deteriorate, such as a decrease in magnetic flux density and an increase in iron loss. Therefore, in the present component system, for example, when the thickness is 0.50 mm, the magnetic flux density B50 in the rolling direction (L direction) L : 1.79T or more, the magnetic flux density B50 in the rolling direction and the width direction (C direction) Average value B50 L + C : 1.75T or more, iron loss W15 / 50 L in the rolling direction: 4.5W / kg or less, average value W15 / 50 L + C of iron loss W15 / 50 in the rolling direction and width direction : It becomes impossible to exhibit the magnetic characteristics represented by 5.0 W / kg or less. The parameter R at the center of the plate thickness is, for example, the difference between the temperature at which the molten steel is injected into the surface of the cooling body that moves and renews and the solidification temperature of the molten steel, and the temperature difference between one surface and the other surface of the slab during solidification. , The amount of sulfide or acid sulfide produced, the cold rolling rate, etc. can be adjusted to obtain a desired value. The lower limit of the parameter R at the center of the plate thickness may be 0.82, 0.85, 0.90, or 0.95. Since it is better that the parameter R at the center of the plate thickness is high, it is not necessary to specify the upper limit value thereof, but it may be, for example, 2.00, 1.90, 1.80, or 1.70.
The crystal orientation of the non-oriented electrical steel sheet according to the present embodiment needs to be controlled as described above in the entire sheet. However, the isotropic texture of the texture of the rolled steel sheet is high in the region close to the rolled surface, and usually decreases as the distance from the rolled surface increases. For example, "Effect of cold rolling conditions on r value of ultra-low carbon cold rolled steel sheet", Hashimoto et al., Iron and Steel, Vol. 76, No. 1 (1990), P.M. At 50, 0.0035% C-0.12% Mn-0.001% P-0.0084% S-0.03% Al-0.11% Ti steel was cold-rolled at a reduction rate of 73%. In the steel sheet obtained by annealing at 750 ° C. for 3 hours, it is shown that the center of thickness is higher at (222), lower at (200), and lower at (110) than the surface layer.
Therefore, if the parameter R is 0.8 or more in the central portion of the plate thickness which is the region farthest from the rolled surface, the isotropic property of the same or higher is achieved in other regions. For the above reasons, the crystal orientation of the non-oriented electrical steel sheet according to the present embodiment is defined at the center of the sheet thickness.
[0023]
{100} crystal orientation strength, {310} crystal orientation strength, {411} crystal orientation strength, {521} crystal orientation strength, {111} crystal orientation strength, {211} crystal orientation strength, {332} at the center of the plate thickness The crystal orientation intensity, {221} crystal orientation intensity, can be measured by an X-ray diffraction method (XRD) or an electron backscatter diffraction (EBSD) method. Specifically, a surface parallel to the rolled surface of the non-directional electromagnetic steel plate and having a depth of about 1/2 of the plate thickness T is made to appear from this rolled surface by a normal method, and the surface is exposed to this surface. By performing XRD analysis or EBSD analysis, each crystal orientation intensity can be measured and the parameter R at the center of the plate thickness can be calculated. Since the diffraction intensity of the X-ray and electron beam from the sample differs for each crystal orientation, the crystal orientation intensity can be obtained based on the relative ratio to the random orientation sample as a reference.
[0024]
Next, the magnetic characteristics of the non-oriented electrical steel sheet according to the embodiment of the present invention will be described. For example, when the thickness of the non-oriented electrical steel sheet according to the present embodiment is 0.50 mm, the magnetic flux density in the rolling direction (L direction) is B50 L : 1.79 T or more, and in the rolling direction and the width direction (C direction). Average value of magnetic flux density B50 B50 L + C : 1.75 T or more, iron loss W15 / 50 L in the rolling direction: 4.5 W / kg or less, average value of iron loss W15 / 50 in the rolling direction and width direction W15 / 50 L + C : It can exhibit magnetic characteristics represented by 5.0 W / kg or less. The magnetic flux density B50 is the magnetic flux density in a magnetic field of 5000 A / m, and the iron loss W15 / 50 is the magnetic flux density of 1.5 T and the iron loss at a frequency of 50 Hz.
[0025]
Next, an example of the method for manufacturing the non-oriented electrical steel sheet according to the present embodiment will be described below. However, as a matter of course, the method for manufacturing the non-oriented electrical steel sheet according to the present embodiment is not particularly limited. The non-oriented electrical steel sheet satisfying the above requirements corresponds to the non-oriented electrical steel sheet according to the present embodiment even if it is obtained by a method other than the manufacturing method exemplified below.
First, the first manufacturing method of the non-oriented electrical steel sheet according to the present embodiment will be exemplified. In the first manufacturing method, continuous casting, hot rolling, cold rolling, finish annealing and the like of molten steel are performed.
[0026]
In molten steel casting and hot rolling, molten steel having the above chemical composition is cast to produce steel ingots such as slabs, and this hot rolling is performed so that the proportion of columnar crystals is 80% or more in terms of area fraction. Moreover, a steel strip having an average crystal grain size of 0.10 mm or more is obtained. At the time of solidification, if the temperature difference between the outermost surface and the inside of the ingot or the temperature difference between one surface of the ingot and the other surface is sufficiently high, the crystal grains solidified on the surface of the ingot are perpendicular to the surface. It grows in the direction and forms columnar crystals. In steel with a BCC structure, columnar crystals grow so that the {100} plane is parallel to the surface of the ingot. Before the columnar crystals develop from the surface to the center of the ingot, or from one surface of the ingot to the other surface, the temperature inside the ingot or the temperature of the other surface of the ingot decreases. When the solidification temperature is reached, crystallization begins inside the ingot or on the other surface of the ingot. Crystals crystallized inside the ingot or on the other surface of the ingot grow equiaxed and have a crystal orientation different from that of columnar crystals.
The columnar crystal ratio can be measured by the following procedure, for example. First, the cross section of the steel strip is polished, and the cross section is etched with a picric acid-based corrosive liquid to reveal a solidified structure. Here, the cross section of the steel strip may be an L cross section parallel to the longitudinal direction of the steel strip or a C cross section perpendicular to the longitudinal direction of the steel strip, but is generally an L cross section. In this cross section, when dendrites develop in the plate thickness direction and penetrate the entire plate thickness, it is determined that the columnar crystal ratio is 100%. If a granular black structure (isoaxial grain) is visible in the cross section other than dendrite, the value obtained by subtracting the thickness of this granular structure from the total thickness of the steel sheet and dividing by the total thickness of the steel sheet is the columnar value of the steel sheet. Let it be the crystalliteity.
In the first manufacturing method, γ → α transformation is likely to occur during cooling after continuous casting of molten steel, but a crystal structure that has undergone γ → α transformation from columnar crystals is also regarded as columnar crystals. By undergoing the γ → α transformation, the {100} <0vw> texture of columnar crystals is further sharpened.
[0027]
The columnar crystals have a {100} <0vw> texture that is desirable for uniformly improving the magnetic properties of grain-oriented electrical steel sheets, particularly the magnetic properties in all directions within the plate surface. The {100} <0vw> texture is a texture in which crystals with a plane parallel to the plate surface {100} plane and a rolling direction <0vw> are developed (v and w are arbitrary real numbers (v and w are arbitrary real numbers). (Except when both v and w are 0)). If the ratio of columnar crystals is less than 80%, it is not possible to obtain an texture in which {100} crystals are developed by finish annealing over the entire sheet thickness direction of the non-oriented electrical steel sheet. In that case, as described above, {100} crystals do not develop at the center of the thickness of the steel sheet, and {111} crystals that are not preferable for the magnetic characteristics develop. The ratio of columnar crystals in the steel strip shall be 80% or more in order to form a texture in which {100} crystals have developed up to the center of the thickness of the steel sheet. As described above, the proportion of columnar crystals in the steel strip can be specified by observing the cross section of the steel strip with a microscope. However, the columnar crystal ratio of the steel strip cannot be accurately measured after the steel strip is subjected to cold rolling or heat treatment, which will be described later. Therefore, in the non-oriented electrical steel sheet according to the present embodiment, the columnar crystal ratio is not particularly specified.
In the first manufacturing method, in order to make the ratio of columnar crystals 80% or more, for example, the temperature difference between one surface of a steel ingot such as a slab during solidification and the other surface is 40 ° C. or more. And. This temperature difference can be controlled by the cooling structure, material, mold taper, mold flux, etc. of the mold. When molten steel is cast under the condition that the ratio of columnar crystals is 80% or more, sulfides or acid sulfides of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn or Cd or these Both are easily formed, and the formation of fine sulfides such as MnS is suppressed.
[0028]
The smaller the average crystal grain size of the steel strip, the larger the number of crystal grains and the larger the area of grain boundaries. In the recrystallization of finish quenching, where crystals grow from within the crystal grains and from the grain boundaries, the crystals that grow from within the crystal grains are {100} crystals that are desirable for magnetic properties, whereas the crystals that grow from the grain boundaries. Is a crystal that is not desirable due to its magnetic properties, such as a {111} <112> crystal. Therefore, the larger the average crystal grain size of the steel strip, the easier it is for {100} crystals that are desirable for magnetic properties to develop in finish annealing, and especially when the average crystal grain size of the steel strip is 0.10 mm or more, excellent magnetism Easy to obtain characteristics. Therefore, the average crystal grain size of the steel strip is set to 0.10 mm or more. The average crystal grain size of the steel strip is adjusted by the temperature difference between the two surfaces of the slab during casting, the average cooling rate in the temperature range of 700 ° C. or higher, the start temperature of hot rolling, the winding temperature, etc. be able to. When the temperature difference between the two surfaces of the slab during casting is 40 ° C or higher and the average cooling rate at 700 ° C or higher is 10 ° C / min or lower, the average crystal grain size of the columnar crystals contained in the steel strip A steel strip having a particle size of 0.10 mm or more can be obtained. Further, when the start temperature of hot rolling is 900 ° C. or lower and the winding temperature is 650 ° C. or lower, the crystal grains contained in the steel strip become unrecrystallized stretched grains, so that the average crystal grain size is 0.10 mm. The above steel strip can be obtained. The average cooling rate in the temperature range of 700 ° C. or higher is the average cooling rate in the temperature range from the casting start temperature to 700 ° C., and the difference between the casting start temperature and 700 ° C. is the casting start temperature. It is a value divided by the time required for cooling from to 700 ° C.
[0029]
The coarse precipitate-forming element is put into the bottom of the last pot before casting in the steelmaking process, and molten steel containing an element other than the coarse precipitate-forming element is injected into the pot to generate coarse precipitate in the molten steel. It is preferable to dissolve the element. As a result, the coarse precipitate-forming element can be made difficult to scatter from the molten steel, and the reaction between the coarse precipitate-forming element and S can be promoted. The last pot before casting in the steelmaking process is, for example, a pot directly above the tundish of a continuous casting machine.
[0030]
When the reduction ratio of cold rolling is more than 90%, a texture that hinders the improvement of magnetic properties, for example, {111} <112> texture, tends to develop during finish annealing. Therefore, the rolling reduction of cold rolling is 90% or less. If the rolling reduction of cold rolling is less than 40%, it may be difficult to ensure the accuracy and flatness of the thickness of the non-oriented electrical steel sheet. Therefore, the rolling reduction of cold rolling is preferably 40% or more.
[0031]
Finish annealing causes primary recrystallization and growth of crystal grains, and the average crystal grain size is 50 μm to 180 μm. By this finish annealing, a texture in which {100} crystals developed suitable for uniformly improving the magnetic properties in all directions in the plate surface can be obtained. In finish annealing, for example, the holding temperature is 750 ° C. or higher and 950 ° C. or lower, and the holding time is 10 seconds or longer and 60 seconds or lower.
[0032]
When the sheet tension for finish annealing is more than 3 MPa, anisotropic elastic strain may easily remain in the non-oriented electrical steel sheet. Since elastic strain with anisotropy deforms the texture, even if a texture with {100} crystals is obtained, this is deformed and the uniformity of magnetic properties in the plate surface is reduced. There is. Therefore, the plate tension for finish annealing is preferably 3 MPa or less. Even when the cooling rate of finish annealing at 950 ° C. to 700 ° C. is more than 1 ° C./sec, elastic strain having anisotropy tends to remain in the non-oriented electrical steel sheet. Therefore, the cooling rate of finish annealing at 950 ° C. to 700 ° C. is preferably 1 ° C./sec or less. Here, the cooling rate is different from the average cooling rate (a value obtained by dividing the difference between the cooling start temperature and the cooling end temperature by the time required for cooling). In consideration of the necessity of always keeping the cooling rate low, in the finish annealing, the cooling rate must always be 1 ° C./sec or less in the temperature range of 950 ° C. to 700 ° C.
[0033]
In this way, the non-oriented electrical steel sheet according to the present embodiment can be manufactured. After finish annealing, an insulating film may be formed by coating and baking.
[0034]
Next, a second manufacturing method of the non-oriented electrical steel sheet according to the embodiment will be described. In the second manufacturing method, rapid solidification of molten steel, cold rolling, finish annealing and the like are performed.
[0035]
In the rapid solidification of molten steel, the molten steel having the above chemical composition is rapidly solidified on the surface of the cooling body that moves and renews, the ratio of columnar crystals is 80% or more in area fraction, and the average crystal grain size is 0.10 mm or more. Get a steel strip. In the second production method, γ → α transformation is likely to occur during cooling of molten steel after rapid solidification, but the crystal structure from columnar crystals to γ → α transformation is also regarded as columnar crystals. By undergoing the γ → α transformation, the {100} <0vw> texture of columnar crystals is further sharpened.
[0036]
The columnar crystals have a {100} <0vw> texture that is desirable for uniformly improving the magnetic properties of grain-oriented electrical steel sheets, particularly the magnetic properties in all directions within the plate surface. The {100} <0vw> texture is a texture in which crystals with a plane parallel to the plate surface {100} plane and a rolling direction <0vw> are developed (v and w are arbitrary real numbers (v and w are arbitrary real numbers). (Except when both v and w are 0)). If the ratio of columnar crystals is less than 80%, it is not possible to obtain an texture in which {100} crystals are developed by finish annealing over the entire sheet thickness direction of the non-oriented electrical steel sheet. In that case, as described above, {100} crystals do not develop at the center of the thickness of the steel sheet, and {111} crystals that are not preferable for the magnetic characteristics develop. The ratio of columnar crystals in the steel strip shall be 80% or more in order to form a texture in which {100} crystals have developed up to the center of the thickness of the steel sheet. The proportion of columnar crystals in the steel strip can be specified by microscopic observation as described above.
In the second production method, in order to increase the proportion of columnar crystals to 80% or more, for example, the temperature of injection into the surface of the moving and renewing cooling body of molten steel is increased by 25 ° C. or more from the solidification temperature. In particular, when the temperature of the molten steel is higher than the solidification temperature by 40 ° C. or more, the ratio of columnar crystals can be made almost 100%. When molten steel is solidified under the condition that the ratio of columnar crystals is 80% or more, sulfides or acid sulfides of Mg, Ca, Sr, Ba, Nd, Pr, La, Ce, Zn or Cd or these. Both of these are easily formed, and precipitation other than these is not excessively generated, and the formation of fine sulfides such as MnS is suppressed.
[0037]
The smaller the average crystal grain size of the steel strip, the larger the number of crystal grains and the larger the area of grain boundaries. In the recrystallization of finish quenching, where crystals grow from within the crystal grains and from the grain boundaries, the crystals that grow from within the crystal grains are {100} crystals that are desirable for magnetic properties, whereas the crystals that grow from the grain boundaries. Is a crystal that is not desirable due to its magnetic properties, such as a {111} <112> crystal. Therefore, the larger the average crystal grain size of the steel strip, the easier it is for {100} crystals that are desirable for magnetic properties to develop in finish annealing, and especially when the average crystal grain size of the steel strip is 0.10 mm or more, excellent magnetism Easy to obtain characteristics. Therefore, the average crystal grain size of the steel strip is set to 0.10 mm or more. The average grain size of the steel strip can be adjusted by the average cooling rate from the completion of solidification to the winding during rapid solidification. Specifically, the average cooling rate from the completion of solidification of the molten steel to the winding of the steel strip is set to 1,000 to 3,000 ° C./min.
[0038]
At the time of rapid solidification, the coarse precipitate-forming element is put into the bottom of the last pot before casting in the steelmaking process, and molten steel containing an element other than the coarse precipitate-forming element is injected into the pot and into the molten steel. It is preferable to dissolve the coarse precipitate-forming element. As a result, the coarse precipitate-forming element can be made difficult to scatter from the molten steel, and the reaction between the coarse precipitate-forming element and S can be promoted. The last pot before casting in the steelmaking process is, for example, the pot directly above the tundish of the casting machine that rapidly solidifies.
[0039]
When the reduction ratio of cold rolling is more than 90%, a texture that hinders the improvement of magnetic properties, for example, {111} <112> texture, tends to develop during finish annealing. Therefore, the rolling reduction of cold rolling is 90% or less. If the rolling reduction of cold rolling is less than 40%, it may be difficult to ensure the accuracy and flatness of the thickness of the non-oriented electrical steel sheet. Therefore, the rolling reduction of cold rolling is preferably 40% or more.
[0040]
Finish annealing causes primary recrystallization and growth of crystal grains, and the average crystal grain size is 50 μm to 180 μm. By this finish annealing, a texture in which {100} crystals developed suitable for uniformly improving the magnetic properties in all directions in the plate surface can be obtained. In finish annealing, for example, the holding temperature is 750 ° C. or higher and 950 ° C. or lower, and the holding time is 10 seconds or longer and 60 seconds or lower.
[0041]
When the sheet tension for finish annealing is more than 3 MPa, anisotropic elastic strain may easily remain in the non-oriented electrical steel sheet. Since elastic strain with anisotropy deforms the texture, even if a texture with {100} crystals is obtained, this is deformed and the uniformity of magnetic properties in the plate surface is reduced. There is. Therefore, the plate tension for finish annealing is preferably 3 MPa or less. Even when the cooling rate of finish annealing at 950 ° C. to 700 ° C. is more than 1 ° C./sec, anisotropy elastic strain may easily remain in the non-oriented electrical steel sheet. Therefore, the cooling rate of finish annealing at 950 ° C. to 700 ° C. is preferably 1 ° C./sec or less. Here, the cooling rate is a concept different from the average cooling rate (a value obtained by dividing the difference between the cooling start temperature and the cooling end temperature by the time required for cooling). In consideration of the necessity of always keeping the cooling rate low, in the finish annealing, the cooling rate must always be 1 ° C./sec or less in the temperature range of 950 ° C. to 700 ° C.
[0042]
In this way, the non-oriented electrical steel sheet according to the present embodiment can be manufactured. After finish annealing, an insulating film may be formed by coating and baking.
[0043]
When the thickness of the non-oriented electrical steel sheet according to the present embodiment is 0.50 mm, for example, the magnetic flux density in the rolling direction (L direction) is B50 L : 1.79 T or more, and the rolling direction and the width direction (C). Average value of magnetic flux density B50 in direction) B50 L + C : 1.75T or more, iron loss W15 / 50 L in rolling direction: 4.5W / kg or less, average value W15 / 50 of iron loss W15 / 50 in rolling direction and width direction 50 L + C : Has high magnetic flux density of 5.0 W / kg or less and low iron loss magnetic properties.
[0044]
Although preferred embodiments of the present invention have been described in detail above, the present invention is not limited to such examples. It is clear that a person having ordinary knowledge in the field of technology to which the present invention belongs can come up with various modifications or modifications within the scope of the technical ideas described in the claims. It is naturally understood that these also belong to the technical scope of the present invention.
Example
[0045]
Next, the non-oriented electrical steel sheet according to the embodiment of the present invention will be specifically described with reference to examples. The examples shown below are merely examples of the non-oriented electrical steel sheets according to the embodiment of the present invention, and the non-oriented electrical steel sheets according to the present invention are not limited to the following examples.
[0046]
(First Test) In
the first test, molten steel having the chemical composition shown in Table 1 was cast to prepare a slab, and the slab was hot-rolled to obtain a steel strip. The blanks in Table 1 indicate that the content of the element was below the detection limit, and the balance was Fe and impurities. The underline in Table 1 indicates that the numerical value is out of the scope of the present invention. Next, cold rolling and finish annealing of the steel strip were performed to produce various non-oriented electrical steel sheets having a thickness of 0.50 mm. Then, the strength of the crystal orientation at the center of the thickness of each non-oriented electrical steel sheet was measured, and the parameter R at the center of the thickness was calculated. The results are shown in Table 2. The underline in Table 2 indicates that the value is out of the scope of the present invention.
[0047]
[table 1]
[0048]
[Table 2]
[0049]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 3. The underline in Table 3 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0050]
[Table 3]
[0051]
As shown in Table 3, the sample No. 11-No. 22 and No. In 11'to 19', the chemical composition was within the range of the present invention, and the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic properties were obtained.
Sample No. 1 to No. In No. 6, since the parameter R at the center of the plate thickness was too small, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. In No. 7, since the S content was too high, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. In No. 8, since the total content of the coarse precipitate-forming element was too low, the total mass of S contained in the sulfide or acid sulfide of the coarse precipitate-forming element was the total mass of S contained in the non-oriented electrical steel sheet. The ratio to is less than 40%, the iron loss W15 / 50 L and the average value W15 / 50 L + C are large, the magnetic flux density B50 L and the average value B50 L + C.Was low. Sample No. In No. 9, since the total content of the coarse precipitate-forming element was too high, the total mass of S contained in the sulfide or acid sulfide of the coarse precipitate-forming element was the total mass of S contained in the non-oriented electrical steel sheet. Although the ratio was 40% or more, Ca formed a large number of inclusions such as CaO, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. It was. Sample No. At 10, the magnetic flux density B50 L and the average value B50 L + C were low because the parameter Q was too large .
[0052]
(Second test) In
the second test, C: 0.0023%, Si: 0.81%, Al: 0.03%, Mn: 0.20%, S: 0.0003% in mass%. And Pr: 0.0138%, and the balance is Fe and impurities (corresponding to samples Nos. 31 to 33 in Table 4-1), C: 0.0021%, Si: 0.83%, Molten steel containing Al: 0.05%, Mn: 0.19%, S: 0.0025% and Pr: 0.0165%, with the balance being Fe and impurities (Sample No. 31'in Table 4-1). (Corresponding to ~ 33') was cast to prepare a slab, and the slab was hot-rolled to obtain a steel strip having a thickness of 2.1 mm. At the time of casting, the temperature difference between the two surfaces of the slab was adjusted to change the ratio of columnar crystals in the steel strip and the average grain size. Table 4-2 shows the temperature difference between the two surfaces, the ratio of columnar crystals, and the average crystal grain size. Then, cold rolling was carried out at a rolling reduction of 78.2% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 850 ° C. for 30 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. This result is also shown in Table 4-2. Underlines in Table 4-2 indicate that the values are outside the scope of the present invention.
[0053]
[Table 4-1]
[0054]
[Table 4-2]
[0055]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 5. The underline in Table 5 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0056]
[Table 5]
[0057]
As shown in Table 5, the sample No. using a steel strip having an appropriate ratio of columnar crystals. 33 and No. At 33', the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic characteristics were obtained.
[0058]
Sample No. using a steel strip with an excessively low proportion of columnar crystals. 31, No. 32, No. 31'and No. In 32', since the parameter R at the center of the plate thickness was out of the range of the present invention, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. ..
[0059]
(Third test) In
the third test, molten steel having the chemical composition shown in Table 6 was cast to prepare a slab, and the slab was hot-rolled to obtain a steel strip having a thickness of 2.4 mm. Obtained. The balance is Fe and impurities, and the underlined values in Table 6 indicate that the values are outside the scope of the present invention. At the time of casting, the ratio of columnar crystals in the steel strip and the average grain size were changed by adjusting the temperature difference between the two surfaces of the slab and the average cooling rate at 700 ° C. or higher. The temperature difference between the two surfaces was 48 ° C to 60 ° C. Sample No. 41, No. 42, No. 41'and No. The average cooling rate of 42'at 700 ° C. or higher was set to 20 ° C./min, and No. 43-No. 45 and No. 43'-No. The average cooling rate of 45'at 700 ° C. or higher was set to 10 ° C./min or less. Table 7 shows the ratio of columnar crystals and the average grain size. Then, cold rolling was carried out at a rolling reduction of 79.2% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 880 ° C. for 45 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are also shown in Table 7. The underline in Table 7 indicates that the value is outside the scope of the present invention.
[0060]
[Table 6]
[0061]
[Table 7]
[0062]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 8. The underline in Table 8 indicates that the value is not in the desired range. That is, Tetsutaba density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L column The underline indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0063]
[Table 8]
[0064]
As shown in Table 8, the sample No. using a steel strip having an appropriate chemical composition, columnar crystal ratio, and average crystal grain size. 44 and No. In 44', since the parameter R at the center of the plate thickness is within the range of the present invention, good magnetic characteristics were obtained.
[0065]
Sample No. using a steel strip whose average grain size is too low. 41, No. 42, No. 41'and No. At 42', the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. 43 and No. At 43', the total content of the coarse precipitate-forming elements was too low, so that the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. 45 and No. At 45', the total content of the coarse precipitate-forming elements was too high, so that the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low.
[0066]
(Fourth Test) In
the fourth test, molten steel having the chemical composition shown in Table 9 was cast to prepare a slab, and the slab was hot-rolled to obtain a steel strip having the thickness shown in Table 10. Obtained. The blanks in Table 9 indicate that the content of the element was below the detection limit, and the balance was Fe and impurities. At the time of casting, the temperature difference between the two surfaces of the slab was adjusted to change the ratio of columnar crystals in the steel strip and the average grain size. The temperature difference between the two surfaces was 51 ° C to 68 ° C. Table 10 also shows the proportion of columnar crystals and the average grain size. Next, cold rolling was carried out at the rolling reduction rates shown in Table 10 to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 830 ° C. for 40 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are also shown in Table 10. The underline in Table 10 indicates that the value is out of the scope of the present invention.
[0067]
[Table 9]
[0068]
[Table 10]
[0069]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 11. The underline in Table 11 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0070]
[Table 11]
[0071]
As shown in Table 11, the sample No. which was cold-rolled with an appropriate rolling reduction amount using a steel strip having an appropriate chemical composition, columnar crystal ratio, and average grain size. 51-No. 55 and No. 51'-No. At 55', the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic characteristics were obtained. Sample No. containing an appropriate amount of Sn or Cu. 53, No. 54, No. 53'and No. At 54', particularly excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L and average value B50 L + C were obtained. Sample No. containing an appropriate amount of Sn and Cu. 55 and No. At 55', even more excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L and average value B50 L + C were obtained.
Sample No. in which the rolling reduction ratio of cold rolling was too high. 56 and No. At 56', the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low.
[0072]
(Fifth test) In
the fifth test, C: 0.0014%, Si: 0.34%, Al: 0.48%, Mn: 1.42%, S: 0.0017% in mass%. And Sr: 0.0179%, and the balance is Fe and impurities (corresponding to samples Nos. 61 to 64 in Table 12-1), C: 0.0015%, Si: 0.35%, Molten steel containing Al: 0.47%, Mn: 1.41%, S: 0.0025% and Sr: 0.0183%, with the balance being Fe and impurities (Sample No. 61'in Table 12-1). A slab was produced by casting (corresponding to ~ 64'), and the slab was hot-rolled to obtain a steel strip having a thickness of 2.3 mm. At the time of casting, the temperature difference between the two surfaces of the slab was 59 ° C., the ratio of columnar crystals in the steel strip was 90%, and the average crystal grain size was 0.17 mm. Then, cold rolling was carried out at a rolling reduction of 78.3% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 920 ° C. for 20 seconds to obtain a non-oriented electrical steel sheet. In the finish annealing, the plate tension and the cooling rate from 950 ° C to 700 ° C were changed. Table 12-2 shows the plate tension and cooling rate. Then, the strength of the crystal orientation of each non-oriented electrical steel sheet was measured, and the parameter R at the center of the sheet thickness was calculated. This result is also shown in Table 12-2.
[0073]
[Table 12-1]
[0074]
[Table 12-2]
[0075]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 13.
[0076]
[Table 13]
[0077]
As shown in Table 13, sample No. 61-No. 64 and No. 61'-No. In 64', the chemical composition was within the range of the present invention, and the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic properties were obtained. Sample No. with a plate tension of 3 MPa or less. 62, No. 63, No. 62'and No. At 63', particularly excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L, and average value B50 L + C were obtained with low elastic strain anisotropy . Sample No. with a cooling rate of 1 ° C./sec or less from 920 ° C. to 700 ° C. 64 and No. At 64', the elastic strain anisotropy was further reduced, and more excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L, and average value B50 L + C were obtained. In the measurement of elastic strain anisotropy, the length of each side is 55 mm, the two sides are parallel to the rolling direction, and the two sides are parallel to the rolling direction (plate width direction). A square sample was cut out from each anisotropy electromagnetic steel plate, and the length of each side after being deformed due to the influence of elastic strain was measured. Then, it was determined how much the length in the direction perpendicular to the rolling direction was larger than the length in the rolling direction.
[0078]
(Sixth Test) In
the sixth test, molten steel having the chemical composition shown in Table 14 was rapidly solidified by the bi-roll method to obtain a steel strip. The blanks in Table 14 indicate that the content of the element was below the detection limit, and the balance was Fe and impurities. Underlines in Table 14 indicate that the values are outside the scope of the present invention. Next, cold rolling and finish annealing of the steel strip were performed to produce various non-oriented electrical steel sheets having a thickness of 0.50 mm. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are shown in Table 15. The underline in Table 15 indicates that the value is outside the scope of the present invention.
[0079]
[Table 14]
[0080]
[Table 15]
[0081]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 16. The underline in Table 16 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W10 / 15 L + C indicates that the value is over 5.0 W / kg.
[0082]
[Table 16]
[0083]
As shown in Table 16, sample No. 111-No. 122 and No. 111'-No. In 119', the chemical composition was within the range of the present invention, and the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic properties were obtained.
Sample No. 101-No. In 106, since the parameter R at the center of the plate thickness was too small, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. In 107, since the S content was too high, the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. In No. 108, the total content of the coarse precipitate-forming elements was too low, so that the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. In 109, the total content of coarse precipitate-forming elements was too high, so iron loss W15 / 50 LThe average value W15 / 50 L + C was large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. At 110, the magnetic flux density B50 L and the average value B50 L + C were low because the parameter Q was too large .
[0084]
(7th test) In
the 7th test, C: 0.0023%, Si: 0.81%, Al: 0.03%, Mn: 0.20%, S: 0.0003% in mass%. And Nd: 0.0138%, and the balance is Fe and impurities (corresponding to samples Nos. 131 to 133 in Table 17-1), C: 0.0021%, Si: 0.83%, Molten steel containing Al: 0.05%, Mn: 0.19%, S: 0.0021% and Nd: 0.0153%, with the balance being Fe and impurities (Sample No. 131'in Table 17-1). (Corresponding to ~ 133') was rapidly solidified by the twin roll method to obtain a steel strip having a thickness of 2.1 mm. At this time, the injection temperature was adjusted to change the proportion of columnar crystals in the steel strip and the average crystal grain size. Table 17 shows the difference between the injection temperature and the solidification temperature, the ratio of columnar crystals, and the average crystal grain size. Then, cold rolling was carried out at a rolling reduction of 78.2% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 850 ° C. for 30 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are also shown in Table 17. The underline in Table 17 indicates that the value is outside the scope of the present invention.
[0085]
[Table 17-1]
[0086]
[Table 17-2]
[0087]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 18. The underline in Table 18 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0088]
[Table 18]
[0089]
As shown in Table 18, the sample No. using a steel strip having an appropriate ratio of columnar crystals. 133 and No. In 133', since the parameter R at the center of the plate thickness is within the range of the present invention, good magnetic characteristics were obtained.
[0090]
Sample No. using a steel strip with an excessively low proportion of columnar crystals. 131, No. 132, No. 131'and No. At 132', the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low.
[0091]
(Eighth Test) In
the eighth test, molten steel having the chemical composition shown in Table 19 was rapidly solidified by the twin roll method to obtain a steel strip having a thickness of 2.4 mm. The balance is Fe and impurities, and the underline in Table 19 indicates that the values are outside the scope of the present invention. At this time, the injection temperature and the average cooling rate from the completion of solidification of the molten steel to the winding of the steel strip were adjusted to change the ratio of columnar crystals in the steel strip and the average crystal grain size. Sample No. 143-No. 145 and No. 143'-No. The injection temperature of 145'was 29 ° C. to 35 ° C. higher than the solidification temperature, and the average cooling rate from the completion of solidification of the molten steel to the winding of the steel strip was 1,500 to 2,000 ° C./min. Sample No. 141, No. 142, No. 141'and No. The injection temperature of 142'was 20 to 24 ° C. higher than the solidification temperature, and the average cooling rate from the completion of solidification of the molten steel to the winding of the steel strip was set to more than 3,000 ° C./min. Table 20 shows the ratio of columnar crystals and the average crystal grain size. Then, cold rolling was carried out at a rolling reduction of 79.2% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 880 ° C. for 45 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are also shown in Table 20. The underline in Table 20 indicates that the value is outside the scope of the present invention.
[0092]
[Table 19]
[0093]
[Table 20]
[0094]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 21. The underline in Table 21 indicates that the value is not in the desired range. That is, Tetsutaba density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L column The underline indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0095]
[Table 21]
[0096]
As shown in Table 21, the sample No. using a steel strip having an appropriate chemical composition, columnar crystal ratio, and average crystal grain size. 144 and No. At 144', the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic characteristics were obtained.
[0097]
Sample No. using a steel strip whose average grain size is too low. 141, No. 142, No. 141'and No. In 142', the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. 143 and No. At 143', the total content of the coarse precipitate-forming elements was too low, so that the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low. Sample No. 145 and No. At 145', the total content of the coarse precipitate-forming elements was too high, so that the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low.
[0098]
(9th Test) In
the 9th test, molten steel having the chemical composition shown in Table 22 was rapidly solidified by the bi-roll method to obtain a steel strip having the thickness shown in Table 23. The blanks in Table 22 indicate that the content of the element was below the detection limit, and the balance was Fe and impurities. At this time, the injection temperature was adjusted to change the proportion of columnar crystals in the steel strip and the average crystal grain size. The injection temperature was 28 ° C. to 37 ° C. higher than the solidification temperature. Table 23 also shows the proportion of columnar crystals and the average grain size. Next, cold rolling was carried out at the rolling reduction rates shown in Table 23 to obtain a steel sheet having a thickness of 0.20 mm. Then, continuous finish annealing was performed at 830 ° C. for 40 seconds to obtain a non-oriented electrical steel sheet. Then, the intensities of the eight crystal orientations of each non-oriented electrical steel sheet were measured, and the parameter R at the center of the plate thickness was calculated. The results are also shown in Table 23. The underline in Table 23 indicates that the value is outside the scope of the present invention.
[0099]
[Table 22]
[0100]
[Table 23]
[0101]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 24. The underline in Table 24 indicates that the value is not in the desired range. That is, the magnetic flux density B50 L underlined column indicates that less than 1.79T, the average value B50 L + C underlined column indicates that less than 1.75 T, iron loss W15 / 50 L underlined column Indicates that the value is over 4.5 W / kg, and the underline in the column of the average value W15 / 50 L + C indicates that the value is over 5.0 W / kg.
[0102]
[Table 24]
[0103]
As shown in Table 24, the sample No. which was cold-rolled with an appropriate rolling reduction amount using a steel strip having an appropriate chemical composition, columnar crystal ratio, and average grain size. 151-No. 154 and No. 151'-No. At 154', the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic characteristics were obtained. Sample No. containing an appropriate amount of Sn or Cu. 153, No. 154, No. 153'and No. At 154', particularly excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L and average value B50 L + C were obtained.
Sample No. in which the rolling reduction ratio of cold rolling was too high. 155 and No. At 155', the iron loss W15 / 50 L and the average value W15 / 50 L + C were large, and the magnetic flux density B50 L and the average value B50 L + C were low.
[0104]
(10th test) In
the 10th test, C: 0.0014%, Si: 0.34%, Al: 0.48%, Mn: 1.42%, S: 0.0017% in mass%. And Sr: 0.0179%, and the balance is Fe and impurities (corresponding to samples Nos. 161 to 164 in Table 25-1), C: 0.0015%, Si: 0.35%, Molten steel containing Al: 0.47%, Mn: 1.41%, S: 0.0026% and Sr: 0.0183%, with the balance being Fe and impurities (Sample No. 161'in Table 25-1). (Corresponding to ~ 164') was rapidly solidified by the twin roll method to obtain a steel strip having a thickness of 2.3 mm. At this time, the injection temperature was set to 32 ° C. higher than the solidification temperature, the ratio of columnar crystals in the steel strip was 90%, and the average crystal grain size was 0.17 mm. Then, cold rolling was carried out at a rolling reduction of 78.3% to obtain a steel sheet having a thickness of 0.50 mm. Then, continuous finish annealing was performed at 920 ° C. for 20 seconds to obtain a non-oriented electrical steel sheet. In the finish annealing, the plate tension and the cooling rate from 920 ° C to 700 ° C were changed. Table 25 shows the plate tension and the cooling rate. Then, the strength of the crystal orientation of each non-oriented electrical steel sheet was measured, and the parameter R at the center of the sheet thickness was calculated. The results are also shown in Table 25.
[0105]
[Table 25-1]
[0106]
[Table 25-2]
[0107]
Then, the magnetic characteristics of each non-oriented electrical steel sheet were measured. The results are shown in Table 26.
[0108]
[Table 26]
[0109]
As shown in Table 26, sample No. 161 to No. 164 and No. 161'-No. At 164', the chemical composition was within the range of the present invention, and the parameter R at the center of the plate thickness was within the range of the present invention, so that good magnetic properties were obtained. Sample No. with a plate tension of 3 MPa or less. 162, No. 163, No. 162'and No. At 163', particularly excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L, and average value B50 L + C were obtained with low elastic strain anisotropy . Sample No. with a cooling rate of 1 ° C./sec or less from 920 ° C. to 700 ° C. 164 and No. At 164', the elastic strain anisotropy was further lowered, and more excellent iron loss W15 / 50 L , average value W15 / 50 L + C , magnetic flux density B50 L, and average value B50 L + C were obtained. In the measurement of elastic strain anisotropy, the length of each side is 55 mm, the two sides are parallel to the rolling direction, and the two sides are parallel to the direction perpendicular to the rolling direction (plate width direction). A quadrilateral sample was cut out from each anisotropy electromagnetic steel plate, and the length of each side after being deformed due to the influence of elastic strain was measured. Then, it was determined how much the length in the direction perpendicular to the rolling direction was larger than the length in the rolling direction.
Industrial applicability
[0110]
The present invention can be used, for example, in the manufacturing industry of non-oriented electrical steel sheets and the utilization industry of non-oriented electrical steel sheets.
The scope of the claims
[Claim 1]
By mass%,
C: 0.0030% or less,
Si: 2.00% or less,
Al: 1.00% or less,
Mn: 0.10% to 2.00%,
S: 0.0030% or less,
Mg, One or more selected from the group consisting of Ca, Sr, Ba, Nd, Pr, La, Ce, Zn and Cd: Totally more than 0.0100% and 0.0250% or less,
Si content (mass%) [Si ], Al content (% by mass) is defined as [Al], Mn content (% by mass) is defined as [Mn], and the parameter Q: 2.00 or less,
Sn: 0.00% to It has a chemical composition represented by 0.40%,
Cu: 0.00% to 1.00%, and the
balance: Fe and impurities,
and has a
{100} crystal orientation strength at the center of the plate thickness and a {310} crystal. Orientation strength, {411} crystal orientation strength, {521} crystal orientation strength, {111} crystal orientation strength, {211} crystal orientation strength, {332} crystal orientation strength, {221} crystal orientation strength are I 100 and I, respectively. 310 , I 411 , I 521 , I 111 , I 211, I 332 , I 221 and the non-oriented electrical steel sheet, characterized in that the parameter R represented by the formula 2 is 0.80 or more.
Q = [Si] + 2 × [Al]-[Mn] (Equation 1)
R = (I 100 + I 310 + I 411 + I 521 ) / (I 111 + I 211 + I 332 + I 221 ) (Equation 2)
[Claim 2]
The non-directional according to claim 1, wherein in the chemical composition,
Sn: 0.02% to 0.40%,
Cu: 0.10% to 1.00%,
or both of them are satisfied. Electrical steel sheet.
[Claim 3]
The method for producing a non-directional electromagnetic steel sheet according to claim 1 or 2
,
wherein the continuous casting step of molten steel, the hot rolling step of the ingot obtained by the continuous casting step, and the
hot rolling step The molten steel has the chemical composition according to claim 1 or 2 , further
comprising a cold rolling step of the obtained steel strip and a finish annealing step of the cold-rolled steel sheet obtained by the cold rolling step.
,
the steel strip, the proportion of the columnar crystals are in an area fraction of 80% or higher and the average crystal grain size is more than 0.10 mm,
the rolling reduction in the cold rolling step is 90% or less
, wherein the A method for manufacturing a non-directional electromagnetic steel sheet.
[Claim 4]
The method for producing a non-oriented electrical steel sheet according to claim 3, wherein in the continuous casting step, the temperature difference between one surface of the steel ingot and the other surface during solidification is 40 ° C. or more.
[Claim 5]
The non-directional electromagnetic wave according to claim 3 or 4, wherein in the hot rolling step, the start temperature of hot rolling is 900 ° C. or lower, and the winding temperature of the steel strip is 650 ° C. or lower. Manufacturing method of steel plate.
[Claim 6]
The non-directionality according to any one of claims 3 to 5, wherein the plate tension in the finish annealing step is 3 MPa or less, and the cooling rate at 950 ° C to 700 ° C is 1 ° C / sec or less . Manufacturing method of electrical steel sheet.
[Claim 7]
The method for producing a non-directional electromagnetic steel sheet according to claim 1 or 2
,
wherein the rapid solidification step of molten steel, the cold rolling step of the steel strip obtained by the rapid solidification step, and the
cold rolling step The
molten steel has the chemical composition according to claim 1 or 2, and the
steel strip has a columnar crystal ratio of 80% or more in terms of area fraction , which comprises a finish annealing step of the obtained cold-rolled steel sheet. A method for producing a non-directional electromagnetic steel sheet, characterized
in
that the average crystal grain size is 0.10 mm or more and the rolling reduction in the cold rolling step is 90% or less .
[Claim 8]
Wherein in the rapid solidification process, using a cooling body moving updated solidifying the molten steel,
the temperature of the molten steel is injected into the cooling body to the moving update, high 25 ° C. or higher than the solidification temperature of the molten steel
characterized in that The method for manufacturing a non-directional electromagnetic steel plate according to claim 7.
[Claim 9]
In the rapid solidification step, the molten steel is solidified using a moving and renewing cooling body, and
the average cooling rate from the completion of solidification of the molten steel to the winding of the steel strip is set to 1,000 to 3,000 ° C./min. The method for manufacturing a non-oriented electrical steel sheet according to claim 7 or 8, wherein the non-oriented electrical steel sheet is manufactured.
[Claim 10]
The non-directionality according to any one of claims 7 to 9, wherein the plate tension in the finish annealing step is 3 MPa or less, and the cooling rate at 950 ° C to 700 ° C is 1 ° C / sec or less . Manufacturing method of electrical steel sheet.
| Section | Controller | Decision Date |
|---|---|---|
| # | Name | Date |
|---|---|---|
| 1 | 202017025929-IntimationOfGrant12-03-2024.pdf | 2024-03-12 |
| 1 | 202017025929-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [19-06-2020(online)].pdf | 2020-06-19 |
| 2 | 202017025929-PatentCertificate12-03-2024.pdf | 2024-03-12 |
| 2 | 202017025929-STATEMENT OF UNDERTAKING (FORM 3) [19-06-2020(online)].pdf | 2020-06-19 |
| 3 | 202017025929-Written submissions and relevant documents [15-01-2024(online)]-1.pdf | 2024-01-15 |
| 3 | 202017025929-REQUEST FOR EXAMINATION (FORM-18) [19-06-2020(online)].pdf | 2020-06-19 |
| 4 | 202017025929-Written submissions and relevant documents [15-01-2024(online)].pdf | 2024-01-15 |
| 4 | 202017025929-PROOF OF RIGHT [19-06-2020(online)].pdf | 2020-06-19 |
| 5 | 202017025929-PRIORITY DOCUMENTS [19-06-2020(online)].pdf | 2020-06-19 |
| 5 | 202017025929-FORM 3 [10-01-2024(online)].pdf | 2024-01-10 |
| 6 | 202017025929-FORM 18 [19-06-2020(online)].pdf | 2020-06-19 |
| 6 | 202017025929-Correspondence to notify the Controller [03-01-2024(online)].pdf | 2024-01-03 |
| 7 | 202017025929-US(14)-ExtendedHearingNotice-(HearingDate-10-01-2024).pdf | 2023-12-12 |
| 7 | 202017025929-FORM 1 [19-06-2020(online)].pdf | 2020-06-19 |
| 8 | 202017025929-US(14)-HearingNotice-(HearingDate-03-01-2024).pdf | 2023-12-05 |
| 8 | 202017025929-DECLARATION OF INVENTORSHIP (FORM 5) [19-06-2020(online)].pdf | 2020-06-19 |
| 9 | 202017025929-ABSTRACT [30-12-2021(online)].pdf | 2021-12-30 |
| 9 | 202017025929-COMPLETE SPECIFICATION [19-06-2020(online)].pdf | 2020-06-19 |
| 10 | 202017025929-CLAIMS [30-12-2021(online)].pdf | 2021-12-30 |
| 10 | 202017025929-FORM-26 [31-08-2020(online)].pdf | 2020-08-31 |
| 11 | 202017025929-COMPLETE SPECIFICATION [30-12-2021(online)].pdf | 2021-12-30 |
| 11 | 202017025929-Verified English translation [06-10-2020(online)].pdf | 2020-10-06 |
| 12 | 202017025929-FER_SER_REPLY [30-12-2021(online)].pdf | 2021-12-30 |
| 12 | 202017025929-FORM 3 [06-11-2020(online)].pdf | 2020-11-06 |
| 13 | 202017025929-OTHERS [30-12-2021(online)].pdf | 2021-12-30 |
| 13 | 202017025929.pdf | 2021-10-19 |
| 14 | 202017025929-FER.pdf | 2021-10-19 |
| 15 | 202017025929-OTHERS [30-12-2021(online)].pdf | 2021-12-30 |
| 15 | 202017025929.pdf | 2021-10-19 |
| 16 | 202017025929-FER_SER_REPLY [30-12-2021(online)].pdf | 2021-12-30 |
| 16 | 202017025929-FORM 3 [06-11-2020(online)].pdf | 2020-11-06 |
| 17 | 202017025929-Verified English translation [06-10-2020(online)].pdf | 2020-10-06 |
| 17 | 202017025929-COMPLETE SPECIFICATION [30-12-2021(online)].pdf | 2021-12-30 |
| 18 | 202017025929-FORM-26 [31-08-2020(online)].pdf | 2020-08-31 |
| 18 | 202017025929-CLAIMS [30-12-2021(online)].pdf | 2021-12-30 |
| 19 | 202017025929-ABSTRACT [30-12-2021(online)].pdf | 2021-12-30 |
| 19 | 202017025929-COMPLETE SPECIFICATION [19-06-2020(online)].pdf | 2020-06-19 |
| 20 | 202017025929-DECLARATION OF INVENTORSHIP (FORM 5) [19-06-2020(online)].pdf | 2020-06-19 |
| 20 | 202017025929-US(14)-HearingNotice-(HearingDate-03-01-2024).pdf | 2023-12-05 |
| 21 | 202017025929-FORM 1 [19-06-2020(online)].pdf | 2020-06-19 |
| 21 | 202017025929-US(14)-ExtendedHearingNotice-(HearingDate-10-01-2024).pdf | 2023-12-12 |
| 22 | 202017025929-Correspondence to notify the Controller [03-01-2024(online)].pdf | 2024-01-03 |
| 22 | 202017025929-FORM 18 [19-06-2020(online)].pdf | 2020-06-19 |
| 23 | 202017025929-FORM 3 [10-01-2024(online)].pdf | 2024-01-10 |
| 23 | 202017025929-PRIORITY DOCUMENTS [19-06-2020(online)].pdf | 2020-06-19 |
| 24 | 202017025929-PROOF OF RIGHT [19-06-2020(online)].pdf | 2020-06-19 |
| 24 | 202017025929-Written submissions and relevant documents [15-01-2024(online)].pdf | 2024-01-15 |
| 25 | 202017025929-Written submissions and relevant documents [15-01-2024(online)]-1.pdf | 2024-01-15 |
| 25 | 202017025929-REQUEST FOR EXAMINATION (FORM-18) [19-06-2020(online)].pdf | 2020-06-19 |
| 26 | 202017025929-STATEMENT OF UNDERTAKING (FORM 3) [19-06-2020(online)].pdf | 2020-06-19 |
| 26 | 202017025929-PatentCertificate12-03-2024.pdf | 2024-03-12 |
| 27 | 202017025929-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [19-06-2020(online)].pdf | 2020-06-19 |
| 27 | 202017025929-IntimationOfGrant12-03-2024.pdf | 2024-03-12 |
| 1 | 2021-07-0612-02-43E_06-07-2021.pdf |