Decarburized annealed steel sheet for grain-oriented electrical steel sheets

Abstract

Provided is a decarburized annealed steel sheet for a grain-oriented electrical steel sheet wherein, with regard to the particle diameter-detected intensity distribution of precipitates for which the equivalent circle diameter D is 50-1000 nm, when the mode diameter of an Al-based precipitate in units of nm is represented as DpAl and the mode diameter of a Nb-based precipitate in units of nm is represented as DpNb, DpNb is 45-250 nm and DpAl-DpNb is 10-50 nm, and the average particle diameter of the decarburized annealed steel sheet is 13-19 μm.

Description

[Technical Field]

[0001] This invention relates to a decarburized annealed steel sheet for grain-oriented electrical steel sheets. This application claims priority based on Japanese Patent Application No. 2024-034154, filed in Japan on March 6, 2024, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] Grain-oriented electrical steel sheet contains 7% by mass or less of Si, {110} <001> It has a secondary recrystallized texture concentrated in the orientation (Goss orientation). <001> Orientation refers to the orientation in which the {110} planes of the crystal are aligned parallel to the rolling plane, and the crystal is <001> This means that the axis is positioned parallel to the rolling direction.

[0003] The magnetic properties of grain-oriented electrical steel sheets are {110} <001> It is greatly influenced by the degree of concentration in a particular direction. In particular, the rolling direction of the steel sheet, which is the main magnetization direction when the steel sheet is used, and the crystal, which is the easy magnetization direction. <001> The relationship with direction is considered important. Therefore, in recent practical grain-oriented electrical steel sheets, the crystal structure <001> The angle between the direction of movement and the rolling direction is controlled to fall within a range of approximately 5°.

[0004] Such precise crystal orientation control is achieved by appropriately dispersing fine precipitates called inhibitors in the steel before finish annealing, and by holding the steel sheet at a high temperature during finish annealing. For example, the inhibitors enhance the selective growth of Goss-oriented grains, and as a result, secondary recrystallization proceeds so that Goss-oriented grains preferentially grow during finish annealing. To date, attempts have been made to highly control inhibitors with the aim of precisely controlling crystal orientation.

[0005] For example, Patent Document 1 discloses the use of MnS as an inhibitor and the performance of two cold rolling processes. Patent documents 2 and 3 disclose controlling MnS+AlN and MnS(and / or MnSe)+Sb as inhibitors, respectively. Patent Document 4 discloses a technique for preferably controlling an inhibitor in order to lower the slab heating temperature for the purpose of reducing manufacturing costs.

[0006] Patent Document 5 discloses controlling the primary recrystallized grain size related to an inhibitor and its dispersion. Patent Documents 6 to 8 disclose adding Nb, V, etc. to a grain-oriented electrical steel sheet.

[0007] In addition, Patent Documents 9 to 11 disclose a technique for improving magnetic strain by forming subgrain boundaries in secondary recrystallized grains by precisely controlling the atmosphere and residence time during finish annealing. In these techniques, a technical concept of expanding the temperature range in which secondary recrystallization progresses in order to form subgrain boundaries is shown, and at the same time, it is shown that an improvement in magnetic flux density can be expected.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Summary of the Invention

Problems to be Solved by the Invention

[0009] In recent years, in the global movement for environmental conservation such as power and energy reduction, the demand for higher efficiency of transformers has been increasing. Under such a social environment, there is also a demand for performance improvement of the grain-oriented electrical steel sheets used for the core materials of transformers. In particular, it is required to increase the magnetic flux density of the grain-oriented electrical steel sheets.

[0010] As a result of the study by the present inventors, it was found that the conventional inhibitor control techniques disclosed in the above Patent Documents 1 to 8 do not fully meet the requirements for grain-oriented electrical steel sheets, and further increase in magnetic flux density is necessary.

[0011] One aspect of the present invention has been made in view of the above problems. One aspect of the present invention aims to provide a decarburized annealed steel sheet for grain-oriented electrical steel sheets capable of increasing the magnetic flux density based on the current situation where an increase in the magnetic flux density of grain-oriented electrical steel sheets is required.

Means for Solving the Problems

[0012] The gist of the present invention is as follows.

[0013] (1) The decarburized annealed steel sheet for grain-oriented electrical steel sheets according to one aspect of the present invention is In mass%, C: 0 to 0.10%, Si: 2.0 to 7.0%, Mn: 0.050 to 1.0%, S: 0 to 0.0350%, Se: 0 to 0.0350%, Total content of S + Se: 0.0030 to 0.0350%, Al: 0.010 to 0.0650%, N: 0.0040~0.0120%, Nb: 0~0.030%, V: 0~0.030%, Mo: 0~0.030%, Ta: 0~0.030%, W: 0~0.030%, Nb+V+Mo+Ta+W total content: 0.0030~0.030%, Cu: 0~0.40%, Bi: 0~0.010%, B: 0~0.080%, P: 0-0.50% Ti: 0~0.0150%, Sn: 0~0.10%, Sb: 0~0.10%, Cr: 0~0.30%, Ni: 0~1.0%, It contains and has a chemical composition consisting of Fe and impurities as the remainder, Precipitates which are the residue obtained by electrolytic extraction of the decarburized annealed steel sheet. Based on a calibration curve created from six types of standard particles with particle sizes of 29 nm, 48 nm, 100 nm, 200 nm, 300 nm, and 500 nm. Particle size-detection intensity distribution measure , The most frequent diameter of Al-based precipitates in units of nm (Dp). Al year, The most frequent diameter of Nb precipitates in units of nm (Dp) Nb In that case, Dp Nb 45~250nm, Dp Al -Dp Nb 10-50nm, Satisfying the conditions, The average particle size of the decarburized annealed steel sheet is 13 to 19 μm. [Effects of the Invention]

[0014] According to the above embodiment of the present invention, a decarburized annealed steel sheet for grain-oriented electrical steel sheets is provided that can increase the magnetic flux density. [Brief explanation of the drawing]

[0015] [Figure 1]This is a schematic diagram of the particle size-detection intensity distribution of precipitates with an equivalent circle diameter D of 50-1000 nm. [Figure 2] This is a flowchart illustrating a method for manufacturing a decarburized annealed steel sheet for grain-oriented electrical steel sheets according to one embodiment of the present invention. [Modes for carrying out the invention]

[0016] A preferred embodiment of the present invention will be described in detail. However, the present invention is not limited to the configuration disclosed in this embodiment, and various modifications are possible without departing from the spirit of the invention. Furthermore, the numerical limits described below include both lower and upper limits. Numerical values ​​indicated as "greater than" or "less than" are not included in the numerical range. Also, "%" in relation to chemical composition means "mass%" unless otherwise specified.

[0017] Furthermore, in the following description, regarding the precipitates in the steel that are characteristic of this embodiment, the term "inhibitor" will be used mainly in descriptions related to the secondary recrystallization mechanism, and the term "precipitate" will be used mainly in descriptions related to the compound phase observed in the microstructure. However, in this embodiment, the terms "inhibitor" and "precipitate" are not used with the intention of strictly distinguishing between them.

[0018] As mentioned above, there is currently a need to increase the magnetic flux density of grain-oriented electrical steel sheets.

[0019] Therefore, the inventors focused on the technical concept of "expanding the secondary recrystallization temperature range" disclosed in the above-mentioned Patent Documents 9 to 11. These Patent Documents 9 to 11 primarily utilize this "expanding the secondary recrystallization temperature range" technique for the formation of subgrain boundaries within secondary recrystallized grains and the associated noise reduction. The inventors considered that further improvement in magnetic flux density would be possible if this "expanding the secondary recrystallization temperature range" technique were optimized to enhance the selectivity of crystal orientation.

[0020] Specifically, we investigated how to effectively expand the secondary recrystallization temperature range by appropriately controlling the inhibitor morphology in the steel, and how to preferentially grow grains with a desirable crystal orientation during the secondary recrystallization process within the expanded temperature range. As a result, we found that by optimally controlling the morphology of precipitates contained in the decarburized annealed steel sheet during the manufacturing process of grain-oriented electrical steel sheets, the secondary recrystallization temperature range can be expanded during finish annealing, Goss-oriented grains can grow preferentially, and the magnetic flux density of the final grain-oriented electrical steel sheet can be increased beyond that of conventional techniques.

[0021] Generally, inhibitors are fine precipitates in steel with a diameter of approximately 1000 nm or less. These inhibitors have a grain boundary pinning effect, suppressing grain growth. When the temperature exceeds approximately 1000°C during finish annealing, these inhibitors dissolve into the αFe phase, the matrix phase, and the grain boundary pinning effect weakens. As a result, abnormal grain growth occurs, a phenomenon known as secondary recrystallization.

[0022] For example, sulfides and selenides are used as Mn-based precipitates, and nitrides are used as Al-based precipitates, serving as major inhibitors. Mn-based inhibitors and Al-based inhibitors (Al-based inhibitors controlled before cold rolling) are mainly used in manufacturing methods where the slab heating temperature before hot rolling is 1300°C or higher (hereinafter sometimes referred to as the "high-temperature slab heating process"). Al-based inhibitors (Al-based inhibitors controlled after cold rolling) are mainly used in manufacturing methods where the slab heating temperature before hot rolling is 1280°C or lower, and nitriding is performed between cold rolling and finish annealing (hereinafter sometimes referred to as the "low-temperature slab heating process"). In addition to the above inhibitors, carbides and nitrides of Nb, V, Mo, Ta, W, etc., are sometimes used as auxiliary inhibitors.

[0023] Traditionally, in order to form inhibitors with appropriate functions within steel, the steel composition and manufacturing conditions have been controlled during the production of grain-oriented electrical steel sheets. In particular, the steel composition, hot rolling conditions, and decarburization annealing conditions have been recognized as manufacturing conditions that greatly influence the morphology of the inhibitors, and these conditions have been precisely controlled.

[0024] In this embodiment, by utilizing Nb group elements and controlling the size and distribution of precipitates (inhibitors) contained in the decarburized annealed steel sheet to an appropriate range, the secondary recrystallization temperature range is expanded during the subsequent finish annealing process, and the selectivity of the crystal orientation as secondary recrystallization progresses is enhanced. Specifically, the above effects are obtained by utilizing precipitates of Nb group elements as relatively fine inhibitors and mainly using AlN as relatively coarse inhibitors, thereby allowing inhibitors to coexist in the decarburized annealed steel sheet with appropriate size and distribution.

[0025] The inventors of this invention estimate that the above effect is obtained through the following mechanism.

[0026] First, let's consider the reason why the temperature range for secondary recrystallization is expanded. As mentioned above, secondary recrystallization occurs because the pinning effect of the grain boundaries weakens as the inhibitor dissolves. During finish annealing, it is thought that fine inhibitors dissolve and disappear earlier than coarse inhibitors. Therefore, when fine and coarse inhibitors coexist, it is thought that the fine inhibitors preferentially disappear early in the heating process of finish annealing. In particular, when at least one element selected from Nb, V, Mo, Ta, and W (Nb group elements) is added, it becomes possible to favorably control the decomposition of fine inhibitors at lower temperatures than conventional inhibitors such as AlN.

[0027] As fine inhibitors dissolve, coarse inhibitors may grow, similar to Ostwald growth. However, the increase in pinning force due to the growth of coarse inhibitors is thought to have a smaller impact than the decrease in pinning force due to the disappearance of fine inhibitors. Therefore, if fine and coarse inhibitors coexist, and the fine inhibitors dissolve earlier than the coarse inhibitors, secondary recrystallization is thought to begin at a relatively low temperature during the heating process of the finish annealing.

[0028] In addition, it is thought that coarse inhibitors remain non-equilibrium dissolved until relatively high temperatures during the heating process of the finish annealing, and that their pinning effect is maintained up to high temperatures. Therefore, when fine and coarse inhibitors coexist, and the coarse inhibitors remain until high temperatures, it is thought that the pinning effect is maintained up to high temperatures, and secondary recrystallization continues up to relatively high temperatures.

[0029] In other words, when fine inhibitors and coarse inhibitors coexist, secondary recrystallization starts at a relatively low temperature during the heating process of the finish annealing and continues up to a relatively high temperature, thus expanding the temperature range in which secondary recrystallization can proceed.

[0030] Next, let's consider the reason why the selectivity of crystal orientation improves. As mentioned above, secondary recrystallization proceeds with the preferential growth of Goss-oriented grains. This preferential growth of Goss-oriented grains is thought to be due to the special characteristics of the grain boundaries (grain boundary properties) and the special characteristics of the grain size (size advantage) of Goss-oriented grains.

[0031] However, the driving force for the preferential growth of Goss-oriented grains is not very strong. Therefore, if grain boundary movement occurs relatively easily even in grains other than Goss-oriented grains during secondary recrystallization, for example, if the inhibitor decomposition is rapid and the grain growth pinning effect is weak, resulting in a relatively high grain growth rate (a relatively high driving force for grain growth), then grains other than Goss-oriented grains will also grow easily. In this case, the preferential growth of Goss-oriented grains is inhibited.

[0032] Therefore, to preferentially grow Goss-oriented grains, the inhibitor decomposition rate should be kept as slow as possible, the grain growth rate during secondary recrystallization should be relatively fast relative to the inhibitor decomposition rate, and secondary recrystallization should be sustained for a long period of time. For example, the heating rate in the temperature range where the inhibitor strength weakens (the temperature range in which the inhibitor dissolves) should be slowed down, the inhibitor dissolution rate should be slowed down, and the resulting secondary recrystallized grain growth rate should be relatively fast relative to the inhibitor decomposition rate. However, this method increases the total finish annealing time, so a decrease in productivity is unavoidable.

[0033] When it is difficult to industrially extend the finish annealing time (when it is difficult to change the heating rate if the maximum temperature reached is the same), even if the heating rate is constant, if the temperature range in which secondary recrystallization proceeds can be expanded by slowing down the decomposition rate of the inhibitor, it is possible to extend the time during which secondary recrystallization proceeds, make the growth rate of secondary recrystallized grains relatively fast, and improve the preferential growth of secondary recrystallized grains without reducing productivity. For example, considering that the entire surface of the grain-oriented electrical steel sheet will eventually be covered with secondary recrystallized grains, it can be understood that extending the time during which secondary recrystallization proceeds leads to an acceleration of the growth rate of secondary recrystallized grains relative to the decomposition rate of the inhibitor.

[0034] In other words, when fine and coarse inhibitors coexist, the temperature range in which the inhibitor decomposition rate is slow expands, and the temperature range in which secondary recrystallization progresses, where the growth rate of secondary recrystallized grains is relatively fast relative to the inhibitor decomposition rate, expands. As a result, it is thought that Goss-oriented grains are more likely to grow preferentially. Consequently, it is thought that it becomes possible to ultimately increase the magnetic flux density.

[0035] In this embodiment, by comprehensively and inseparably controlling the steel composition, casting conditions, hot rolling conditions, hot-rolled sheet annealing conditions, cold rolling conditions, and decarburization annealing conditions, relatively fine precipitates and relatively coarse precipitates are made to coexist in an appropriate size and distribution in the decarburized annealed steel sheet after the decarburization annealing process. In particular, in this embodiment, the morphology of the precipitates is preferably controlled by adding auxiliary inhibitor-forming elements (Nb group elements).

[0036] In this embodiment, the morphology of the precipitates described above is defined based on the decarburized annealed steel sheet.

[0037] The decarburized annealed steel sheet for grain-oriented electrical steel sheets according to this embodiment will be described in detail below.

[0038] The decarburized annealed steel sheet according to this embodiment is, by mass %, C: 0~0.10%, Si: 2.0~7.0%, Mn: 0.050~1.0%, S: 0~0.0350%, Se: 0~0.0350%, S+Se total content: 0.0030~0.0350%, Al: 0.010~0.0650%, N: 0.0040~0.0120%, Nb: 0~0.030%, V: 0~0.030%, Mo: 0~0.030%, Ta: 0~0.030%, W: 0~0.030%, Nb+V+Mo+Ta+W total content: 0.0030~0.030%, Cu: 0~0.40%, Bi: 0~0.010%, B: 0~0.080%, P: 0-0.50% Ti: 0~0.0150%, Sn: 0~0.10%, Sb: 0~0.10%, Cr: 0~0.30%, Ni: 0~1.0%, contains a chemical composition consisting of the remainder being Fe and impurities, Among the precipitates that are the residues of electropolishing a decarburized annealed steel sheet, for the particle size-detection intensity distribution of precipitates with a circle equivalent diameter D of 50 to 1000 nm, let the most frequent diameter of the Al-based precipitate be Dp in units of nm Al and let the most frequent diameter of the Nb-based precipitate be Dp in units of nm Nb when Dp Nb is 45 to 250 nm, Dp Al - Dp Nb is 10 to 50 nm, satisfies and the average particle size of the decarburized annealed steel sheet is 13 to 19 μm.

[0039] 1. Chemical Composition The chemical composition of the decarburized annealed steel sheet according to this embodiment may be a general chemical composition used for grain-oriented electrical steel sheets.

[0040] Incidentally, it is rare for known literature on grain-oriented electrical steel sheets to describe the chemical composition of the decarburized annealed steel sheet, which is an intermediate product.

[0041] The decarburized annealed steel sheet according to this embodiment includes basic elements as a chemical composition, and may include selected elements as necessary, with the remainder consisting of Fe and impurities.​​​​​​​​​Silicon (Si) increases the electrical resistance of grain-oriented electrical steel sheets, thereby reducing iron loss. If the Si content is less than 2.0%, austenite transformation occurs during finish annealing, damaging the crystal orientation of the grain-oriented electrical steel sheet. On the other hand, if the Si content exceeds 7.0%, cold workability decreases, making the sheet more prone to cracking during cold rolling. Therefore, the Si content of decarburized annealed steel sheets should be between 2.0% and 7.0%. The preferred lower limit of the Si content is 2.50%, and more preferably 3.0%. The preferred upper limit of the Si content is 4.50%, and more preferably 4.0%.

[0044] Mn: 0.050~1.0% Manganese (Mn) combines with S and Se to precipitate as MnS and MnSe, functioning as inhibitors. To favorably control the morphology of these inhibitors (precipitates), the Mn content of the decarburized annealed steel sheet should be between 0.050% and 1.0%. If the Mn content is below 0.050%, the amount of MnS and MnSe that function as inhibitors will be insufficient, thus inhibiting the proper progression of secondary recrystallization. Conversely, if the Mn content exceeds 1.0%, the amount of MnS and MnSe that function as inhibitors will be excessive, also inhibiting the proper progression of secondary recrystallization. In this embodiment, some of the inhibitory functions may be carried out by carbides, nitrides, or carbonitrides of Nb group elements. In this case, the amount of MnS and MnSe that precipitate as inhibitors may be controlled to be lower. Therefore, the upper limit of the Mn content is preferably 0.50%, and more preferably 0.20%.

[0045] S: 0~0.0350% Se: 0~0.0350% S+Se total content: 0.0030~0.0350% Sulfur (S) and selenium (Se) combine with Mn to precipitate as MnS and MnSe, respectively, and function as inhibitors. To favorably control the morphology of these inhibitors (precipitates), the S content of the decarburized annealed steel sheet should be 0 to 0.0350%, the Se content 0 to 0.0350%, and the total S+Se content 0.0030 to 0.0350%. A total S and Se content of 0.0030 to 0.0350% is preferable because it stabilizes secondary recrystallization. In this embodiment, some of the inhibitor functions may be carried out by carbides, nitrides, or carbonitrides of Nb group elements. In this case, the amount of MnS and MnSe precipitated as inhibitors may be controlled to be smaller. Therefore, the upper limit of the total S and Se content is preferably 0.0250%, and more preferably 0.010%. Furthermore, if S and Se remain in the steel after finish annealing, they can form compounds that degrade iron loss. Therefore, it is preferable to remove S and Se from the steel through purification during finish annealing to reduce their content.

[0046] Here, "the total content of S and Se is 0.0030 to 0.0350%" means that the decarburized annealed steel sheet may contain only either S or Se in its chemical composition, and its content may be between 0.0030 and 0.0350%. Alternatively, it may contain both S and Se, and their total content may be between 0.0030 and 0.0350%.

[0047] Al: 0.010~0.0650% Aluminum (Al) combines with nitrogen (N) to precipitate as AlN or (Al,Si)N, functioning as inhibitors. To favorably control the morphology of these inhibitors (precipitates), the Al content of the decarburized annealed steel sheet should be between 0.010% and 0.0650%. If the Al content is 0.010% or higher, AlN and (Al,Si)N precipitate in favorable forms through nitriding treatment in the low-temperature slab heating process, and secondary recrystallization is particularly stable in the high-temperature range. If the Al content is below 0.010%, the amount of AlN and (Al,Si)N that function as inhibitors precipitated is insufficient, hindering the proper progress of secondary recrystallization. If the Al content exceeds 0.0650%, the amount of AlN and (Al,Si)N that function as inhibitors precipitates is excessive, also hindering the proper progress of secondary recrystallization. The lower limit of the Al content is preferably 0.020%, and more preferably 0.0250%. From the viewpoint of stability during secondary recrystallization, the upper limit of the Al content is preferably 0.040%, and more preferably 0.030%.

[0048] N: 0.0040~0.0120% Nitrogen (N) combines with Al to precipitate as AlN or (Al,Si)N, functioning as an inhibitor. The N content of decarburized annealed steel sheets should be between 0.0040% and 0.0120%. In low-temperature slab heating processes, N may be added to the steel during the manufacturing process through nitriding. If the N content exceeds 0.0120%, blistering, a type of defect, is more likely to occur in the steel sheet. The upper limit of the N content is preferably 0.010%, and more preferably 0.0090%. N is purified in the finish annealing process, and after the finish annealing process, the N content becomes 0.0050% or less.

[0049] Nb+V+Mo+Ta+W total content: 0.0030~0.030% Nb: 0~0.030% V: 0~0.030% Mo: 0~0.030% Ta: 0~0.030% W: 0~0.030% Niobium (Nb), vanadium (V), molybdenum (Mo), tantalum (Ta), and tungsten (W) precipitate as auxiliary inhibitors such as carbides, nitrides, and carbonitrides, and function favorably as inhibitors. Specifically, they favorably extend the temperature range over which secondary recrystallization can proceed. Therefore, the Nb content is 0-0.030%, the V content is 0-0.030%, the Mo content is 0-0.030%, the Ta content is 0-0.030%, the W content is 0-0.030%, and the total Nb+V+Mo+Ta+W content is 0.0030-0.030%. The lower limit of the Nb, V, Mo, Ta, and / or W content is preferably 0.0040%, and more preferably 0.0050%. Furthermore, the upper limit of the content of Nb, V, Mo, Ta, and / or W is preferably 0.020%, and more preferably 0.010%.

[0050] In this embodiment, Nb, V, Mo, Ta, and W may be collectively referred to as "Nb group elements."

[0051] The decarburized annealed steel sheet according to this embodiment contains, as Nb group elements, one or more elements selected from the Nb group elements consisting of Nb, V, Mo, Ta, and W, in a total of 0.0030 to 0.030 mass%.

[0052] When Nb group element precipitates are used as inhibitors, if the total content of Nb group elements in the decarburized annealed steel sheet is 0.030% or less (preferably 0.0030% to 0.030%), the morphology of the Nb group element precipitates is preferably controlled, and the secondary recrystallization temperature range is preferably expanded. As a result, Goss-oriented grains grow preferably, and the magnetic flux density of the resulting grain-oriented electrical steel sheet is preferably increased.

[0053] The reason why precipitates of Nb group elements function favorably as inhibitors is not clear, but it is thought to be as follows: Carbides, nitrides, or carbonitrides of Nb group elements are thought to precipitate non-equilibrium during the cooling process from high temperatures and act as precipitation nuclei for MnS and AlN that precipitate thereafter. Therefore, compared to cases where Nb group elements are not present, when Nb group elements are present, there are many more precipitation sites for MnS and AlN, and as a result, MnS and AlN are more likely to form as fine precipitates. In the decarburized annealed steel sheet according to this embodiment, the secondary recrystallization temperature range is expanded by allowing fine and coarse inhibitors to coexist, and precipitates of Nb group elements are thought to be particularly effective in expanding the secondary recrystallization temperature range to the lower temperature side. In this embodiment, it is important to control the manufacturing conditions so as to increase the difference between the most frequent diameter of Nb-based precipitates and the most frequent diameter of Al-based precipitates.

[0054] The total content of Nb group elements is preferably 0.0040% or more, and more preferably 0.0050% or more. Furthermore, the total content of Nb group elements is preferably 0.020% or less, and more preferably 0.010% or less. If the total content of Nb group elements falls below 0.0030%, there will be insufficient precipitates of Nb group elements that act as precipitation nuclei, making it difficult for MnS and AlN to become finely ground. On the other hand, if the total content of Nb group elements exceeds 0.030%, the precipitation temperature range of the Nb group element precipitates will be high, and the precipitates of Nb group elements will tend to be coarse and low in density. In addition, the difference between the precipitation temperature range of Nb group element precipitates and the precipitation temperature range of MnS and AlN will be large, making it difficult for the Nb group element precipitates to effectively act as precipitation nuclei for the refinement of MnS and AlN.

[0055] Here, "total content of Nb group elements is 0.0030 to 0.030%" means that the decarburized annealed steel sheet contains at least one element selected from the group consisting of Nb, V, Mo, Ta, and W as part of its chemical composition, and its content may be 0.0030 to 0.030%. Alternatively, it means that the decarburized annealed steel sheet contains at least two or more elements selected from the group consisting of Nb, V, Mo, Ta, and W, and its total content may be 0.0030 to 0.030%.

[0056] The decarburized annealed steel sheet according to this embodiment may contain impurities in its chemical composition. "Impurities" refer to elements that are introduced from raw materials such as ore and scrap, or from the manufacturing environment, during the industrial production of steel. The upper limit of the total impurity content may be, for example, 5%.

[0057] Furthermore, the decarburized annealed steel sheet according to this embodiment may contain optional elements in addition to the basic elements and impurities described above. For example, instead of a portion of the remaining Fe described above, C, Cu, Bi, B, P, Ti, Sn, Sb, Cr, Ni, etc. may be included as optional elements. These optional elements may be included according to their purpose. Therefore, there is no need to limit the lower limit of these optional elements, and the lower limit may be 0%. Moreover, even if these optional elements are included as impurities, the above effects will not be impaired.

[0058] C: 0~0.10% Carbon (C) is an effective element for controlling the primary recrystallization structure during the manufacturing process. In particular, C forms carbides and carbonitrides with elements such as Nb, making it effective in controlling the primary recrystallization structure. Therefore, the C content of the slab is preferably 0.0010 to 0.10%. However, excessive C content in the final product adversely affects the magnetic properties. Therefore, the C content of decarburized annealed steel sheet should be 0 to 0.10%. The preferred upper limit for C content is 0.0850% and 0.0750%. Note that C is purified in the finish annealing process described later, and after the finish annealing process, it becomes 0.0050% or less. When C is included, considering the productivity in industrial production, the C content may be greater than 0% or greater than 0.0010%.

[0059] Cu: 0~0.40% Bi: 0~0.010% B: 0~0.080% P: 0-0.50% Ti: 0~0.0150% Sn: 0~0.10% Sb: 0~0.10% Cr: 0~0.30% Ni: 0~1.0% Copper (Cu), bismuth (Bi), boron (B), phosphorus (P), titanium (Ti), tin (Sn), antimony (Sb), chromium (Cr), and nickel (Ni) may be included according to known purposes. There is no need to set a lower limit for the content of these selected elements, and the lower limit may be 0%.

[0060] In grain-oriented electrical steel sheets, relatively large changes in chemical composition (reduction in content) occur through decarburization annealing and purification annealing during secondary recrystallization. For some elements, purification annealing can reduce the content to levels undetectable by general analytical methods (less than 1 ppm). However, the above chemical composition refers to the chemical composition of decarburized annealed steel sheets.

[0061] The chemical composition of the decarburized annealed steel sheet according to this embodiment can be measured using general analytical methods for steel. For example, the chemical composition of the decarburized annealed steel sheet can be measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry). Specifically, the chemical composition can be determined by measuring a 35 mm square test piece taken from the decarburized annealed steel sheet using ICP-AES under conditions based on a pre-established calibration curve. C and S can be measured using the combustion-infrared absorption method, and N can be measured using the inert gas fusion-thermal conductivity method.

[0062] 2. Precipitate Next, we will describe the precipitates contained in the decarburized annealed steel sheet according to this embodiment.

[0063] The precipitates (inhibitors) contained in the decarburized annealed steel sheet according to this embodiment may be precipitates formed from elements contained in the decarburized annealed steel sheet. For example, Mn-based precipitates (Mn-containing precipitates) may be sulfides or selenides, Al-based precipitates (Al-containing precipitates) may be nitrides, and Nb-based precipitates (Nb group element-containing precipitates) may be carbides, nitrides, or carbonitrides. In addition to these inhibitors, auxiliary inhibitors may include compounds of Nb group elements other than Nb, compounds of arbitrary elements such as Bi and B, or composite compounds with the above elements.

[0064] The precipitates to be controlled in the decarburized annealed steel sheet according to this embodiment are precipitates with an equivalent circular diameter D of 50 to 1000 nm. "Equivalent circular diameter" refers to the diameter of a circle when the area of ​​the precipitate is converted to a circle of the same area. This equivalent circular diameter is equivalent to the equivalent spherical diameter.

[0065] Precipitates with an equivalent circle diameter D smaller than 50 nm in decarburized annealed steel sheets currently have little effect in expanding the temperature range for secondary recrystallization. The reason for this is not clear, but it is thought that precipitates with an equivalent circle diameter D smaller than 50 nm in the decarburized annealed steel sheet change or disappear in subsequent processes and are less likely to function as inhibitors during finish annealing.

[0066] Specifically, precipitates with an equivalent circle diameter D smaller than 50 nm tend to reduce the size of precipitates such as AlN that precipitate in subsequent processes. Therefore, they do not contribute to increasing the difference in decomposition temperature between precipitates that decompose at relatively low temperatures and precipitates that decompose at relatively high temperatures during finish annealing. In the decarburized annealed steel sheet according to this embodiment, it is important to ensure a difference between the most frequent diameter of Nb-based precipitates and the most frequent diameter of Al-based precipitates. Accordingly, in the decarburized annealed steel sheet according to this embodiment, the size and distribution of precipitates with an equivalent circle diameter D of 50 nm or more are controlled. Furthermore, by considering processes after the decarburization annealing process, it is expected that precipitates with an equivalent circle diameter D of less than 50 nm will function as inhibitors in the future.

[0067] Furthermore, precipitates with an excessively large equivalent circle diameter D may adversely affect the growth of secondary recrystallized grains in the final stage of secondary recrystallization. Also, the formation of precipitates with an excessively large equivalent circle diameter D may reduce the number of precipitates (number density) contained in the decarburized annealed steel sheet. In addition, precipitates with an excessively large equivalent circle diameter D are less likely to function as inhibitors. For this reason, it is preferable that the equivalent circle diameter D of the precipitates be 1000 nm or less on average. In the decarburized annealed steel sheet according to this embodiment, the size and distribution of precipitates with an equivalent circle diameter D of 50 to 1000 nm are controlled to have the effect of expanding the secondary recrystallization temperature range.

[0068] In the decarburized annealed steel sheet according to this embodiment, among the precipitates which are the residue obtained by electrolytic extraction of the decarburized annealed steel sheet, the particle size-detection intensity distribution of precipitates with an equivalent circle diameter D of 50 to 1000 nm is as follows: The most frequent diameter of Al-based precipitates in units of nm (Dp). Al year, The most frequent diameter of Nb precipitates in units of nm (Dp) Nb In that case, Dp Nb 45~250nm, Dp Al -Dp Nb 10-50nm, It satisfies the condition.

[0069] Figure 1 shows a schematic diagram of the particle size-detection intensity distribution of precipitates with an equivalent circle diameter D of 50 to 1000 nm. In Figure 1, Dp Al and Dp Nb To give an example:

[0070] Dp Nb However, above 250 nm, it is unsuitable because the number of fine precipitates necessary to expand the secondary recrystallization temperature range decreases. Dp Nb The upper limit is preferably 200 nm, and more preferably 100 nm. On the other hand, Dp Nb When the wavelength is less than 45 nm, as mentioned above, the effect of expanding the secondary recrystallization temperature range is small. Nb The lower limit is preferably 50 nm, and more preferably 65 nm.

[0071] Dp Al -Dp Nb If the value is less than 10 nm, the balance between relatively fine inhibitors and relatively coarse inhibitors is undesirable, so the secondary recrystallization temperature range is not sufficiently expanded, which is inappropriate. Dp Al -Dp Nb The lower limit is preferably 15 nm, and more preferably 20 nm. On the other hand, Dp Al -Dp Nb If the value exceeds 50 nm, the coarse inhibitor is too large, causing non-uniform growth of the primary recrystallized grains during normal grain growth, resulting in a mixed grain structure before secondary recrystallization, making it unsuitable. Dp Al -Dp Nb The upper limit is preferably 45 nm, and more preferably 40 nm.

[0072] The particle size-detection intensity distribution of precipitates with an equivalent circle diameter D of 50 to 1000 nm can be determined as follows.

[0073] For example, the method described in Japanese Patent No. 6572598 may be used. First, precipitates are electrolytically extracted from the decarburized annealed steel sheet. The electrolytic extraction conditions can be as follows: for example, a constant current electrolytic extraction (500 mA - 2 hours) can be performed using a solution prepared by adding a dispersant such as a surfactant (for example, sodium dodecyl sulfate with a molecular weight of 288.38 g / mol) to an acetylacetone-based electrolyte in appropriate amounts. The electrolytic extraction should be performed in such a way that the amount of electrolytic material extracted from the decarburized annealed steel sheet is 1 g or more.

[0074] The extraction residue (precipitation) should be recovered from the electrolytic extract. The size and distribution of this recovered precipitate should be measured by the FFF-ICP-MS (Field Flow Fractionation - Inductively Coupled Plasma - Mass Spectrometry) method. For particle separation conditions using the FFF method, refer to Japanese Patent No. 6572598 mentioned above.

[0075] Note that each parameter can be changed depending on the particle size and type being measured. Here is an example: The FFF instrument should be a Wyatt Eclipse AF4 instrument (Wyatt Technology Europe, Germany). For the dispersion solution of the measurement sample, an aqueous solution of sodium dodecyl sulfate at a concentration of 300 mg / mL should be used. For the cell, an asymmetric diamond-type channel spacer with a channel length of 275 mm and a thickness of 350 μm should be used. As the separation membrane, a regenerated cellulose ultrafiltration membrane with a molecular weight of 30 kDa should be used.

[0076] Before adding the extraction residue (precipitation) recovered from the electrolytic extract, it is necessary to create a calibration curve by correlating particle size with the time until particle detection using standard samples with known particle sizes. The type and number of standard samples should be selected according to the particle size distribution of the extraction residue to be measured, but for example, standard particles of polystyrene latex with particle sizes of 29 to 500 nm can be selected.

[0077] The size of the standard particles must be directly confirmed beforehand using a TEM (Transmission Electron Microscope) or similar device. A minimum of 500 measurements should be performed. The longest side of each standard particle should be measured, and the average value should be calculated. Regarding the types of particle sizes used, for example, six different particle sizes such as 29 nm, 48 nm, 100 nm, 200 nm, 300 nm, and 500 nm can be used.

[0078] The actual separation conditions should be as follows. First, for stabilization before focusing, the eluent flow (channel flow) of the FFF instrument (hereinafter referred to as channel flow) should be 1.0 mL / min and the cross flow 0.5 mL / min for 1 minute. Then, for focusing before sample injection, the focus flow should be 3.0 mL / min for 1 minute. Next, during focusing, the sample should be injected at 0.2 mL / min for 2 minutes. The focusing time after sample injection should be 1 minute. After that, the flow path should be switched, the focus flow should be stopped, and the channel flow should be 1.0 mL / min, and the cross flow should be injected while decreasing the flow rate in direct proportion from 0.5 mL / min to 0.05 mL / min over 35 minutes. A calibration curve should be created by correlating the time from when the injection started until particles were detected with the average value of the particle size of the standard particles that had been measured in advance. The maximum time for particle detection should be 35 minutes, and the injection volume of the liquid in which the sample is dispersed should be 0.1 to 0.4 mL.

[0079] After creating the calibration curve as described above, the extraction residue (precipitate) recovered from the electrolytic extract is then added back into the apparatus. The apparatus settings parameters should be the same as described above.

[0080] In this way, the particle size of nanoparticles contained in the nanoparticle dispersion sample to be measured can be determined.

[0081] Furthermore, the effluent from the FFF instrument (a solution containing precipitates separated by size) can be analyzed for its components using inductively coupled plasma mass spectrometry (ICP-Mass).

[0082] Using the particle size distribution data calculated from the measurement results of the FFF-ICP-MS method, a distribution of particle size and ICP-MS detection intensity (Al detection intensity and Nb group element detection intensity) can be created. From this particle size-detection intensity distribution, Dp Al and Dp Nb We just need to find that.

[0083] In this embodiment, Nb-based precipitates refer to precipitates containing at least one element selected from the Nb group elements Nb, V, Mo, Ta, and W, and Dp Nb This refers to the most frequent diameter of the Nb precipitate. In this embodiment, the "most frequent diameter" corresponds to the particle size at which the detection intensity value is highest in the particle size-detection intensity distribution described above.

[0084] Note that the above Dp Al , Dp Nb Calculations such as these are preferably performed after smoothing the measurement data from the FFF-ICP-MS method. For example, the simple moving average method can be used to smooth the measurement data from the FFF-ICP-MS method.

[0085] 3.Average particle size Next, the average grain size of the decarburized annealed steel sheet according to this embodiment will be described.

[0086] The average particle size of the decarburized annealed steel sheet according to this embodiment is 13 to 19 μm. In the decarburized annealed steel sheet according to this embodiment, relatively fine precipitates and relatively coarse precipitates coexist in an appropriate size and distribution, so the average particle size of the decarburized annealed steel sheet (steel sheet after primary recrystallization) is preferably reduced in diameter.

[0087] The average particle size of the decarburized annealed steel sheet is preferably 18 μm or less, and more preferably 17 μm. The lower limit of the average particle size is not particularly limited. For example, the average particle size of the decarburized annealed steel sheet may be 13 μm or more.

[0088] The average grain size of the decarburized annealed steel sheet according to this embodiment can be determined based on the cutting method of JIS G0551 (2013). For example, an L-shaped cross-section (a cross-section normalized to the direction perpendicular to the rolling direction) of the decarburized annealed steel sheet can be photographed using an optical microscope at a magnification of 200x, and the grain size of the crystalline structure of this cross-section can be measured along the thickness direction of the sheet based on the above cutting method. This measurement can be performed at least five times at different measurement locations to determine the average grain size.

[0089] 4. Plate thickness The thickness of the decarburized annealed steel sheet according to this embodiment is not particularly limited. The decarburized annealed steel sheet according to this embodiment is subjected to subsequent processes, namely the annealing separating agent coating process and the finish annealing process, to finally be finished into a grain-oriented electrical steel sheet. Therefore, considering the general manufacturing conditions for grain-oriented electrical steel sheets, the thickness of the decarburized annealed steel sheet can be 0.10 to 0.50 mm. However, it is not limited to this thickness, and known thicknesses or thicknesses used in practical applications may be adopted.

[0090] 5. Manufacturing method Next, a method for manufacturing a decarburized annealed steel sheet for grain-oriented electrical steel according to one embodiment of the present invention will be described. Note that the method for manufacturing the decarburized annealed steel sheet according to this embodiment is not limited to the method described below. The manufacturing method described below is one example for manufacturing the decarburized annealed steel sheet according to this embodiment.

[0091] Figure 2 is a flowchart illustrating the manufacturing process of a decarburized annealed steel sheet according to this embodiment. Figure 2 also shows the manufacturing process of a grain-oriented electrical steel sheet using this decarburized annealed steel sheet. As shown in Figure 2, the manufacturing method of a decarburized annealed steel sheet according to this embodiment comprises a casting process, a hot rolling process, a hot-rolled sheet annealing process, a cold rolling process, and a decarburization annealing process. The conditions controlled in these processes will be described in detail later.

[0092] Furthermore, the processes following the annealing separation agent application process shown in Figure 2, namely the annealing separation agent application process and the finish annealing process, are manufacturing processes for grain-oriented electrical steel sheets (finish annealed steel sheets). The effect of the decarburized annealed steel sheet according to this embodiment can be confirmed in the final product, the grain-oriented electrical steel sheet, so the conditions to be controlled in these processes will also be described later.

[0093] The method for manufacturing a decarburized annealed steel sheet according to this embodiment comprises a casting step, a hot rolling step, a hot rolled sheet annealing step, a cold rolling step, and a decarburization annealing step. In the casting process, In mass%, C: 0.0010~0.10%, Si: 2.0~7.0%, Mn: 0.050~1.0%, S: 0~0.0350%, Se: 0~0.0350%, S+Se total content: 0.0030~0.0350%, Al: 0.010~0.0650%, N: 0.0040~0.0120%, Nb: 0~0.030%, V: 0~0.030%, Mo: 0~0.030%, Ta: 0~0.030%, W: 0~0.030%, Nb+V+Mo+Ta+W total content: 0.0030~0.030%, Cu: 0~0.40%, Bi: 0~0.010%, B: 0~0.080%, P: 0-0.50% Ti: 0~0.0150%, Sn: 0~0.10%, Sb: 0~0.10%, Cr: 0~0.30%, Ni: 0~1.0%, Molten steel having a chemical composition containing and the remainder consisting of Fe and impurities is cast and formed into a slab. In the hot rolling process, the slab after the casting process is heated, roughly rolled, and then finish-rolled to form a hot-rolled steel sheet. In the hot-rolled sheet annealing process, the hot-rolled steel sheet after the hot-rolling process is annealed to obtain a hot-rolled annealed steel sheet. In the cold rolling process, the hot-rolled and annealed steel sheet, after the hot-rolled sheet annealing process, is rolled to form a cold-rolled steel sheet. In the decarburization annealing process, the cold-rolled steel sheet after the cold-rolling process is decarburized and annealed to obtain a decarburized annealed steel sheet.

[0094] Furthermore, in the method for manufacturing decarburized annealed steel sheets according to this embodiment, In the hot rolling process, During the slab heating process before rough rolling, the soaking temperature of the slab should be set to over 1030°C but less than 1180°C, and the soaking time should be set to over 70 minutes. During rough rolling, the rolling temperature is set to 940-1070°C and the reduction ratio to 82-95%. In the hot-rolled sheet annealing process, the maximum temperature reached is 1000-1140°C, and during the cooling process, the average cooling rate from 1050-900°C is 1-5°C / second, and the average cooling rate from 900-500°C is 10-50°C / second. In the cold rolling process, the reduction ratio is set to 80-95%. In the decarburization annealing process, the average heating rate during the heating process may be set to 15 to 2000°C / second over a period of 200 to 750°C, and the maximum temperature reached may be set to 800 to 900°C.

[0095] To control the size and distribution of precipitates in decarburized annealed steel sheets, it is necessary to control the steel composition, casting conditions, hot rolling conditions, hot-rolled sheet annealing conditions, cold rolling conditions, and decarburization annealing conditions, respectively. In particular, it is important to control the steel composition, slab heating conditions, rough rolling temperature, and rough rolling reduction ratio, as well as the cooling process after hot-rolled sheet annealing, the cold rolling reduction ratio, and the heating process during decarburization annealing.

[0096] Furthermore, the slab heating described above does not require temporarily increasing the heating temperature during the heating process; instead, it is sufficient to perform soaking at a predetermined temperature for a predetermined time. In this case, the soaking temperature of the slab refers to the surface temperature of the slab, and the soaking time refers to the time the slab's surface temperature is maintained after reaching the soaking temperature. For example, although it is also affected by the steel composition and heating rate, if the slab's surface temperature is maintained for the soaking time after reaching the soaking temperature, the precipitation state of precipitates from the surface to the center of the slab will be uniformly controlled.

[0097] The important manufacturing conditions for the decarburized annealed steel sheet manufacturing method according to this embodiment are described below. Other manufacturing conditions can be those of conventional known grain-oriented electrical steel sheets.

[0098] (Casting process) In the casting process, a slab is prepared. Since the chemical composition other than C (carbon) hardly changes from the slab to the decarburization annealing process, the chemical composition of the slab should be the same as the target decarburized annealed steel sheet (the chemical composition of the decarburized annealed steel sheet described above), excluding C (carbon). The C content of the slab should be 0.0010 to 0.10%.

[0099] An example of a slab manufacturing method is as follows: Molten steel is produced (melted). A slab is manufactured using this molten steel. For example, the slab may be manufactured by continuous casting. Alternatively, an ingot may be manufactured using molten steel, and the ingot may be rolled into a slab. The thickness of the slab is, for example, 150 to 350 mm. Preferably, the thickness of the slab is 220 to 280 mm. A so-called thin slab with a thickness of 10 to 70 mm may be used as the slab.

[0100] (Hot rolling process) The hot rolling process involves heating a slab to a predetermined temperature and performing hot rolling (rough rolling and finish rolling) to obtain a hot-rolled steel sheet.

[0101] For example, in the hot rolling process, the slab after the casting process is heated, rough rolling is performed, and then finish rolling is performed to produce a hot-rolled steel sheet with a predetermined thickness of 1.8 to 3.5 mm. After the finish rolling is completed, the hot-rolled steel sheet is wound up at a predetermined temperature.

[0102] During the hot rolling process, when heating the slab after the casting process, the following conditions must be met.

[0103] When heating the slab before rough rolling, the slab should be heated so that the soaking temperature is between 1030°C and 1180°C, and the soaking time is more than 70 minutes. At this time, it is preferable that a portion of the precipitates contained in the slab are dissolved (for example, based on the precipitates contained in the slab at room temperature after the casting process, it is preferable that 12 to 85 volume percent of the precipitates are dissolved).

[0104] By preferably dissolving some of the precipitates contained in the slab before rough rolling, it becomes easier to ultimately achieve a favorable balance between the amount of relatively coarse precipitates that remain dissolved after the slab heating stage (undissolved precipitates) and the amount of relatively fine precipitates that do not precipitate during the slab heating stage but precipitate after hot rolling (re-precipitation precipitates).

[0105] Furthermore, if Nb group elements are not present, precipitates such as AlN and MnS that are dissolved during slab heating tend to precipitate unevenly in subsequent processes. Therefore, in this embodiment, Nb group elements are included in the slab. Nb group elements assist in the uniform reprecipitation of AlN and MnS, and at the same time contribute to the favorable distribution of relatively fine inhibitors and relatively coarse inhibitors, thereby favorably enhancing the preferential growth of secondary recrystallization.

[0106] Furthermore, as described above, in this embodiment, the soaking time of the slab is set to more than 70 minutes. In conventional manufacturing methods, the soaking time during slab heating was limited to about 60 minutes at most, from a cost perspective. For example, in conventional manufacturing methods where the slab does not contain 0.0030% or more of Nb group elements, even if the soaking time of the slab is extended, there is no significant change in the reprecipitation state of dissolved AlN and MnS in subsequent processes, and the soaking time of the slab does not have a significant effect on the magnetic properties of the final product.

[0107] However, if the slab contains 0.0030% or more of Nb group elements, and the soaking time of the slab exceeds 70 minutes, the Nb-based precipitates among the precipitates contained in the slab will be completely dissolved or nearly dissolved during slab heating. In this case, precipitates such as AlN and MnS will re-precipitation in a favorable state in subsequent processes, and as a result, secondary recrystallization will preferably occur.

[0108] Therefore, in this embodiment, the slab contains Nb group elements, and in the hot rolling process, when heating the slab before rough rolling, the soaking temperature during slab heating should be set to over 1030°C and less than 1180°C, and the soaking time should be set to over 70 minutes. In this case, it is preferable to dissolve a portion of the precipitates contained in the slab (for example, based on the precipitates contained in the slab at room temperature after the casting process, it is preferable to dissolve 12 to 85 volume percent of the precipitates).

[0109] When the Nb group element content is within the above range, even if the slab heating temperature is 1100°C or higher, it is possible to ultimately achieve the coexistence of fine and coarse inhibitors. For example, if the slab heating temperature is high and the solution treatment of AlN and MnS is promoted during the slab heating stage, these AlN and MnS particles tend to reprecipitate coarsely in subsequent processes. However, when the Nb group element content is within the above range, the Nb group element precipitates act as precipitation nuclei for MnS and AlN, reducing the size of the reprecipitated AlN and MnS. Furthermore, because the precipitation nose of Nb group element precipitates (carbonitrides) is at a lower temperature than the precipitation noses of AlN and MnS, the Nb group element precipitates themselves tend to precipitate as even finer precipitates than AlN and other elements.

[0110] Therefore, when the Nb group element content is within the above range, the upper limit temperature during slab soaking should be less than 1180°C. While higher soaking temperatures promote the solution formation of precipitates, when the Nb group element content meets the above range, the effect of the Nb group element precipitates makes it easier to achieve a coexistence of fine and coarse inhibitors.

[0111] Similarly, when the Nb group element content is within the above range, the lower limit temperature for slab soaking should be above 1030°C. Note that as the soaking temperature decreases, the solution formation of precipitates is also suppressed; however, when the Nb group element content satisfies the above range, it ultimately becomes possible to have both fine and coarse inhibitors coexist.

[0112] The mechanism by which the above effects are obtained is thought to be related to the fact that precipitates of Nb group elements (carbonitrides) precipitate more easily than MnS and AlN (in particular, MnS is difficult to precipitate without support such as dislocation proliferation due to rolling, and when it does precipitate, it becomes larger in size), and that precipitates of Nb group elements function as precipitation nuclei in the precipitation of MnS and AlN, suppressing the coarsening of re-precipitated AlN and MnS.

[0113] Furthermore, when the Nb group element content is within the above range, a soaking time of 70 minutes or less is too short, making it difficult to control the solution state of the precipitate to an equilibrium state. While the upper limit of the soaking time is not particularly limited, it may be set to 2 hours considering productivity in industrial production.

[0114] Controlling the "solution state of precipitates before rough rolling" to the above conditions makes it easier to achieve a favorable balance between the amount of relatively coarse precipitates that remain precipitated during the slab heating stage (undissolved precipitates) and the amount of relatively fine precipitates that precipitate after hot rolling (re-precipitation precipitates).

[0115] The soaking temperature of the slab mentioned above represents the surface temperature of the slab, and the soaking time of the slab represents the time the slab's surface temperature is maintained after reaching the soaking temperature. For example, although it is also affected by the steel composition and heating rate, if the slab's surface temperature is maintained for the soaking time mentioned above after reaching the soaking temperature, the precipitation state of precipitates will be uniformly controlled from the surface to the center of the slab.

[0116] In the hot rolling process, hot rolling is carried out following the slab heating described above. Generally, hot rolling is divided into rough rolling and finish rolling. In this embodiment, in order to control the size and distribution of precipitates contained in the steel sheet after the decarburization annealing process, it is important to control the "solution state of precipitates before rough rolling" described above, and then control each condition from hot rolling onward.

[0117] In the hot rolling process, the following conditions must be met when rough rolling is performed after heating the slab.

[0118] When rough-rolling a heated slab, the rolling temperature should be controlled to 940-1070°C and the reduction ratio to 82-95%. The rough-rolling temperature is defined as the average value of the start and end temperatures of the rough-rolling process.

[0119] By setting the reduction ratio within the above range, processing-induced precipitation occurs, making it possible to precipitate fine and abundant precipitates. If the reduction ratio in rough rolling is smaller than the lower limit above, the introduction of dislocations due to the rolling process will decrease, and the number of precipitation sites that can undergo processing-induced precipitation will decrease, resulting in larger particle sizes for the precipitates. On the other hand, there is no particular upper limit to the reduction ratio in rough rolling, but it is reasonable to set it at 95% considering the performance of the rolling mill, etc.

[0120] The reduction ratio for rough rolling mentioned above refers to the cumulative reduction ratio during rough rolling. Specifically, the reduction ratio for rough rolling is defined as follows: Rough rolling reduction ratio (cumulative reduction ratio) (%) = (1 - "steel plate thickness after rough rolling" / "steel plate thickness before rough rolling") × 100

[0121] Furthermore, if the rolling temperature for rough rolling is higher than the upper limit mentioned above, precipitates of MnS, AlN, and Nb group elements will precipitate at a higher temperature than or near the precipitation nose, resulting in a larger critical radius for precipitation of precipitates that re-precipitation during hot rolling. Consequently, the size difference between these precipitates and the relatively coarse precipitates (undissolved precipitates) that precipitate from the slab heating stage becomes smaller. On the other hand, there is no particular lower limit to the rolling temperature for rough rolling, but since the slab hardens and its rollability decreases at lower temperatures, it is advisable to roll at, for example, 940°C or higher.

[0122] Furthermore, when the chemical composition preferably contains Nb group elements, during rough rolling, precipitates of Nb group elements (especially carbides and nitrides) precipitate in addition to MnS and AlN. These Nb group element precipitates act as precipitation nuclei for MnS and AlN that precipitate later, resulting in finer reprecipitation of MnS and AlN. Therefore, when the chemical composition preferably contains Nb group elements, the control conditions such as rough rolling temperature and rough rolling reduction ratio should be controlled as described above.

[0123] When Nb group elements are suitably included, the reason why the conditions of the hot rolling process should be controlled as described above is as follows: When Nb group elements are included, MnS and AlN re-precipitation occurs more finely due to the precipitates of Nb group elements, so the particle size of the re-precipitationd precipitates becomes smaller compared to when Nb group elements are not included. Therefore, it becomes easier to favorably balance the amount of precipitates between the relatively coarse precipitates that remain precipitated during the slab heating stage (undissolved precipitates) and the precipitates that do not precipitate during the slab heating stage but precipitate relatively finely after hot rolling (re-precipitationd precipitates). For this reason, it is considered that the conditions of the hot rolling process should be controlled as described above.

[0124] For example, if the solution state of precipitates is not favorably controlled when Nb group elements are present (for example, if the "solution rate of precipitates before rough rolling" is lower than 12 volume%), the precipitates will not be sufficiently dissolved at the time of slab heating, similar to the case where Nb group elements are not present, and fewer fine precipitates will re-precipitation during hot rolling. Therefore, it will be difficult to sufficiently expand the secondary recrystallization temperature range during finish annealing. Also, if the solution state of precipitates is not favorably controlled when Nb group elements are present (for example, if the "solution rate of precipitates before rough rolling" is higher than 85 volume%), most of the precipitates will be easily dissolved at the time of slab heating, similar to the case where Nb group elements are not present, and fewer relatively coarse precipitates (undissolved precipitates) will remain in the slab. Therefore, it will be difficult to sufficiently expand the secondary recrystallization temperature range during finish annealing.

[0125] Furthermore, the reason why the rough rolling reduction ratio should be controlled as described above when Nb group elements are suitably included, compared to when Nb group elements are not suitably included, is thought to be as follows: When Nb group elements are included, precipitates of Nb group elements tend to precipitate finely in the steel, so the number of fine precipitates contained in the steel is greater even before rough rolling compared to when Nb group elements are not included. Therefore, when Nb group elements are included, there are more precipitation sites for precipitates, and processing-induced precipitation is more likely even when the reduction ratio is reduced. For this reason, it is thought that the rough rolling reduction ratio should be controlled as described above.

[0126] When Nb group elements are present, if the reduction ratio during rough rolling is less than 82%, the introduction of dislocations due to the rolling process will be reduced, similar to when Nb group elements are not present, resulting in fewer precipitation sites that can be precipitated by the process, and thus the particle size of the precipitate will increase. When Nb group elements are present, the upper limit of the reduction ratio during rough rolling is preferably 93%.

[0127] Furthermore, the reason why the rough rolling temperature should be controlled as described above when Nb group elements are suitably included, compared to when Nb group elements are not suitably included, is thought to be as follows: When Nb group elements are included, as mentioned above, the number of fine precipitates contained in the steel increases even before rough rolling, compared to when Nb group elements are not included. Therefore, when Nb group elements are included, there are more precipitation sites for precipitates, and the precipitates that re-precipitation during hot rolling tend to be finer. For this reason, it is thought that the rough rolling temperature should be controlled as described above.

[0128] When Nb group elements are present, if the rough rolling temperature is higher than 1070°C, all precipitates, including MnS, AlN, and Nb group elements, will undergo processing-induced precipitation at a temperature higher than the precipitation nose of the precipitates. This increases the critical precipitation radius of the precipitates that re-precipitation during hot rolling. As a result, the size difference between the relatively coarse precipitates (undissolved precipitates) that have precipitated since the slab heating stage becomes smaller. When Nb group elements are present, the upper limit of the rough rolling temperature is preferably 1065°C, and more preferably 1040°C.

[0129] Furthermore, although the reason why Nb group elements promote the fine precipitation of precipitates is not clear, it is thought to be as follows.

[0130] During rough rolling, the steel sheet temperature drops rapidly over time. Therefore, the rough rolling process is considered to be in a non-equilibrium state. Even in temperature ranges where all MnS and AlN would precipitate in an equilibrium state, dissolved MnS and AlN may exist in a non-equilibrium state. For example, because the rough rolling process is in a non-equilibrium state, dissolved MnS and AlN are thought to exist even in temperature ranges where Nb group elements precipitate. Therefore, when Nb group elements precipitate during rough rolling, these precipitates are thought to act as precipitation nuclei for MnS and AlN that precipitate later, causing fine precipitates of MnS and AlN. Specifically, compared to the case where Nb group element precipitates are not present, the presence of Nb group element precipitates many more precipitation sites for MnS and AlN, resulting in finer precipitates of MnS and AlN.

[0131] Furthermore, when precipitates of Nb group elements that acted as precipitation nuclei for MnS and AlN are covered with MnS or AlN, the further growth of those Nb group element precipitates is suppressed. In this case, the Nb group elements that would have been consumed in the growth of the precipitates are thought to precipitate as new, fine precipitates. These new, fine precipitates of Nb group elements are thought to act as new precipitation nuclei for MnS and AlN, contributing to the further fine precipitation of MnS and AlN. Thus, precipitates of Nb group elements are thought to synergistically contribute to the fine precipitation of MnS and AlN.

[0132] When the above-mentioned conditions in the hot rolling process are satisfied, and the conditions after the hot rolling process are also satisfied, the size and distribution of precipitates are preferably controlled. As a result, after the decarburization annealing process, the particle size-detection intensity distribution of the precipitates is controlled within the above range.

[0133] Furthermore, the slab soaking temperature during slab heating before rough rolling, and the rolling temperature during rough rolling, as described above, are temperatures that are controlled with a specific purpose. These temperatures are not due to the natural temperature drop that occurs when the slab is removed from the slab heating furnace and subjected to rough rolling. For example, in general operation, the slab soaking temperature and rough rolling temperature are not controlled with a specific purpose. Normally, if the slab soaking temperature is high, the rough rolling temperature will also be high, and if the slab soaking temperature is low, the rough rolling temperature will also be low. On the other hand, in this embodiment, the slab soaking temperature and rough rolling temperature described above are controlled with a specific purpose. For example, even if the slab soaking temperature is high within the above range, the rough rolling temperature is controlled to remain within the above range, and similarly, even if the slab soaking temperature is low within the above range, the rough rolling temperature is controlled to remain within the above range.

[0134] Furthermore, the conditions for finish rolling in the hot rolling process are not particularly limited; normal hot rolling conditions can be used.

[0135] (Hot-rolled sheet annealing process) The hot-rolled sheet annealing process is a process in which hot-rolled steel sheets are annealed after the hot-rolling process to obtain hot-rolled annealed steel sheets. Hot-rolled sheet annealing is generally performed to control the steel sheet structure, such as the recrystallization rate, residual strain, and grain size, and to favorably adjust the morphology of precipitates in the steel.

[0136] In the hot-rolled sheet annealing process, the following conditions must be met when annealing the hot-rolled steel sheet after hot rolling.

[0137] During hot-rolled sheet annealing, the maximum temperature reached should be 1000-1140°C, and during the cooling process, the average cooling rate should be controlled to 1-5°C / second between 1050-900°C and 10-50°C / second between 900-500°C.

[0138] When the maximum temperature reached during hot-rolled sheet annealing is within the above range, Al-based precipitates (such as AlN) are preferably dissolved. Furthermore, the dissolved Al-based precipitates tend to reprecipitate in the temperature range of 1050 to 900°C during the cooling process. Therefore, controlling the average cooling rate in the 1050 to 900°C range during the cooling process allows for favorable control of Al-based precipitate reprecipitation. For example, if the average cooling rate in the cooling process is within the above range of 1050 to 900°C, Al-based precipitates preferentially reprecipitate more coarsely than Nb-based precipitates. Since the coarse Al-based precipitates remain non-equilibrium dissolved until relatively high temperatures during the heating process of finish annealing, the secondary recrystallization temperature range is preferably extended to higher temperatures.

[0139] Similarly, when the maximum temperature reached during hot-rolled sheet annealing is within the above range, Nb precipitates are preferably dissolved. The dissolved Nb precipitates tend to reprecipitate in the 900-500°C temperature range during the cooling process. Therefore, controlling the average cooling rate in the 900-500°C temperature range during the cooling process allows for favorable control of Nb precipitate reprecipitation. For example, if the average cooling rate in the 900-500°C temperature range during the cooling process is within the above range, fine Nb precipitates can be preferably formed. Since the fine Nb precipitates begin to dissolve from relatively low temperatures during the heating process of finish annealing, the secondary recrystallization temperature range is preferably extended to the lower temperature side.

[0140] The average cooling rate between 1050°C and 900°C during the cooling process is calculated by dividing the temperature difference from the highest temperature to 900°C by the cooling time from the highest temperature to 900°C when the highest temperature reached is between 1000°C and 1050°C, and by the cooling time from 1050°C to 900°C when the highest temperature reached is between 1050°C and 1140°C. Similarly, the average cooling rate between 900°C and 500°C during the cooling process is calculated by dividing the temperature difference from 900°C to 500°C (400°C) by the cooling time from 900°C to 500°C.

[0141] (Cold rolling process) The cold rolling process involves taking the hot-rolled and annealed steel sheet obtained in the hot-rolled sheet annealing process and cold-rolling it multiple times (two or more times) via annealing (intermediate annealing) to obtain a cold-rolled steel sheet with a thickness of, for example, 0.10 to 0.50 mm.

[0142] In the cold rolling process, when rolling the hot-rolled and annealed steel sheet after the hot-rolled sheet annealing process, the reduction ratio of the cold rolling should be controlled to 80-95%.

[0143] The cold rolling reduction ratio mentioned above refers to either the cumulative cold rolling reduction ratio without intermediate annealing, or the cumulative cold rolling reduction ratio after intermediate annealing. Specifically, the cold rolling reduction ratio is defined as follows: Cold rolling reduction ratio (cumulative reduction ratio) (%) = (1 - "steel sheet thickness after cold rolling" / "steel sheet thickness before cold rolling (or after intermediate annealing)") × 100

[0144] When the reduction ratio of cold rolling is within the above range, the primary recrystallized texture after decarburization annealing is preferably controlled. Specifically, the primary recrystallized texture is such that, during secondary recrystallization, ideal Goss-oriented grains (ideal {110} <001> The texture becomes such that orientation grains (which have an orientation) preferentially grow (specifically, in the primary recrystallized texture, {111} <112> ya{411} <148> (The crystal orientation represented by becomes the dominant orientation.) As a result, it is preferable because it is easier to obtain a secondary recrystallized texture in the final product in which ideal Goss orientation grains have preferentially grown.

[0145] (Decarburization annealing process) The decarburization annealing process involves performing decarburization annealing on cold-rolled steel sheets obtained in the cold-rolling process to obtain decarburized annealed steel sheets in which primary recrystallization has occurred. By performing decarburization annealing on cold-rolled steel sheets, carbon (C) contained in the cold-rolled steel sheets is removed. Decarburization annealing is preferably performed in a humid atmosphere in order to remove the "C" contained in the cold-rolled steel sheets.

[0146] In the decarburization annealing process, the following conditions must be met when annealing the cold-rolled steel sheet after the cold-rolling process.

[0147] During decarburization annealing, the average heating rate during the heating process should be set to 15-2000°C / second between 200-750°C, and the maximum temperature reached should be controlled to 800-900°C.

[0148] When the average heating rate during the decarburization annealing heating process is within the above range, the primary recrystallized texture after decarburization annealing is preferably controlled. Specifically, the primary recrystallized texture becomes one in which ideal Goss orientation grains preferentially grow during secondary recrystallization. As a result, the magnetic flux density B8 of the final product is preferably high. Furthermore, when the maximum temperature reached during decarburization annealing is within the above range, the primary recrystallized grain size can be controlled to a suitable range. As a result, after the Nb-based precipitates decompose on the lower temperature side of the finish annealing heating process, secondary recrystallized grains with Goss orientation can grow sufficiently, which is preferable.

[0149] The average heating rate between 200°C and 750°C during the heating process is calculated by dividing the temperature difference (550°C) from 200°C to 750°C by the heating time required to reach that temperature.

[0150] As described above, the method for manufacturing a decarburized annealed steel sheet according to this embodiment comprises a casting step, a hot rolling step, a hot-rolled sheet annealing step, a cold rolling step, and a decarburization annealing step. In the decarburized annealed steel sheet manufactured by comprehensively controlling the above conditions in each step, the size and distribution of precipitates are preferably controlled, and the particle size-detection intensity distribution of the precipitates is controlled within the above range. As a result, the secondary recrystallization temperature range is expanded during finish annealing, the selective growth of Goss-oriented grains is enhanced, and the magnetic flux density of the grain-oriented electrical steel sheet is improved.

[0151] For example, as described above, in the manufacturing method of decarburized annealed steel sheets according to this embodiment, the amount of relatively coarse precipitates (undissolved precipitates) that remain precipitated during the slab heating stage is controlled mainly by the slab soaking temperature and slab soaking time during slab heating before rough rolling, and the amount of relatively fine precipitates (re-precipitated precipitates) is controlled by the subsequent manufacturing conditions, thereby controlling each characteristic of the decarburized annealed steel sheet within the above range. As a result, the secondary recrystallization temperature range is expanded during finish annealing, the selective growth of Goss-oriented grains is improved, and the magnetic flux density of the grain-oriented electrical steel sheet is improved.

[0152] 6. How to use decarburized annealed steel sheets The effect of the decarburized annealed steel sheet according to this embodiment can be confirmed in the final product, the grain-oriented electrical steel sheet. Therefore, from the perspective of how to use the decarburized annealed steel sheet according to this embodiment, the manufacturing process of the grain-oriented electrical steel sheet following the decarburization annealing process will be described.

[0153] The manufacturing method for grain-oriented electrical steel sheets includes an annealing and separating agent application step and a finish annealing step. Additionally, if necessary, it may include nitriding, insulating film formation, and magnetic domain control steps. These steps can utilize known general process conditions. Below, a manufacturing method applying nitriding as a low-temperature slab heating process will be described as an example.

[0154] (nitriding treatment) Nitriding is performed to adjust the strength of the inhibitor during secondary recrystallization. In nitriding, the nitrogen content of the steel sheet can be increased to approximately 40-300 ppm at any time between the start of the decarburization annealing described above and the start of secondary recrystallization during the finish annealing described later. Examples of nitriding treatments include annealing the steel sheet in an atmosphere containing a gas with nitriding ability such as ammonia, or finishing annealing a decarburized annealed steel sheet coated with an annealing separator containing a powder with nitriding ability such as MnN.

[0155] (Annealing separating agent application process) The annealing separation agent application process involves applying an annealing separation agent to a decarburized annealed steel sheet. Examples of annealing separation agents that can be used include those primarily composed of MgO or alumina.

[0156] After applying the annealing release agent, the decarburized annealed steel sheet is wound into a coil and then finished annealed in the next finish annealing process.

[0157] (Finishing annealing process) The finish annealing process involves applying a finish annealing to a decarburized annealed steel sheet coated with an annealing separating agent to induce secondary recrystallization. This process allows secondary recrystallization to proceed while the growth of primary recrystallized grains is suppressed by an inhibitor, thus {110} <001> This method prioritizes the growth of azimuthal particles, thereby improving magnetic flux density.

[0158] When using the decarburized annealed steel sheet according to this embodiment, the secondary recrystallization temperature range is expanded during finish annealing, resulting in a level of {100} not previously seen. <011> Preferential growth of oriented grains occurs, resulting in a dramatic increase in magnetic flux density. Additionally, abnormal grain growth of secondary recrystallized grains occurs during finish annealing, and after finish annealing, these secondary recrystallized grains occupy the entire surface of the plate. The few secondary recrystallized grains cover the entire surface of the steel plate, and the grain size of each secondary recrystallized grain increases.

[0159] Furthermore, in the finish annealing process, the finish annealing conditions for "expanding the secondary recrystallization temperature range" disclosed in the above-mentioned Patent Documents 9 to 11 may be applied as needed. By using the decarburized annealed steel sheet according to this embodiment and applying the finish annealing conditions disclosed in Patent Documents 9 to 11, the secondary recrystallization temperature range can be further preferably expanded.

[0160] The following insulating film formation and magnetic domain control steps use the crystal orientation {110}. <001> From the perspective of integration, this process is not necessary. However, it is a process that is commonly used in grain-oriented electrical steel sheets to improve practical magnetic properties. (Insulating film formation process) The insulating coating formation process is a process of forming an insulating coating on grain-oriented electrical steel sheets (finish-annealed steel sheets) after the finish annealing process. An insulating coating mainly composed of phosphate and colloidal silica, or an insulating coating mainly composed of alumina sol and boric acid, can be formed on the steel sheet after finish annealing.

[0161] (Magnetic domain control process) The magnetic domain control process is a process that subdivides the magnetic domains of the grain-oriented electrical steel sheet. This process is carried out at an appropriate time after cold rolling. For example, local minute strains or local grooves can be formed in the grain-oriented electrical steel sheet using known methods such as laser, plasma, mechanical methods, or etching.

[0162] 7. Grain-oriented electrical steel sheet obtained using the decarburized annealed steel sheet according to this embodiment A brief description will be given of grain-oriented electrical steel sheets manufactured using decarburized annealed steel sheets according to this embodiment.

[0163] In the decarburized annealed steel sheet according to this embodiment, relatively fine and relatively coarse precipitates coexist in a favorable size and distribution. Therefore, in the grain-oriented electrical steel sheet obtained using the decarburized annealed steel sheet according to this embodiment, Goss-oriented grains preferentially grow, and the magnetic flux density is favorably increased. Furthermore, since the grain-oriented electrical steel sheet manufactured using the decarburized annealed steel sheet according to this embodiment does not suffer deterioration of other properties due to the increased magnetic flux density, it can be used for the same applications as conventional steel sheets.

[0164] The grain-oriented electrical steel sheet manufactured using the decarburized annealed steel sheet according to this embodiment contains, by mass fraction, Si (silicon): 2.0 to 7.0% as a basic element (major alloying element).

[0165] Furthermore, impurities may be present. "Impurities" refer to elements introduced during the industrial production of steel, either from the raw materials (ore or scrap) or from the manufacturing environment. The total impurity content may be capped at, for example, 5%.

[0166] Furthermore, in addition to the basic elements and impurities mentioned above, optional elements may also be included. For example, instead of a portion of the remaining Fe mentioned above, optional elements such as Nb, V, Mo, Ta, W, C, Mn, S, Se, Al, N, Cu, Bi, B, P, Ti, Sn, Sb, Cr, Ni, etc., may be included. These optional elements may be included according to their purpose. Therefore, there is no need to limit the lower limit of these optional elements, and the lower limit may be 0%. Also, these optional elements may be included as impurities.

[0167] In grain-oriented electrical steel sheets, relatively large changes in chemical composition (reduction in content) occur through decarburization annealing and purification annealing during secondary recrystallization. Depending on the element, the content may be reduced to a level undetectable by general analytical methods (less than 1 ppm) through purification annealing. Generally, the chemical composition of the final product differs from that of the starting material slab. However, the arbitrary elements mentioned above are elements that remained in the final product from those contained in the slab, and the content of each element will not exceed the aforementioned content range for the slab, but will be within the content range corresponding to the content in the slab and subsequent manufacturing processes.

[0168] The above chemical composition is that of grain-oriented electrical steel sheet. If the grain-oriented electrical steel sheet used as a measurement sample has an insulating coating or the like on its surface, the coating or the like should be removed by a known method before measuring the chemical composition.

[0169] The grain-oriented electrical steel sheet manufactured using the decarburized annealed steel sheet according to this embodiment may have an intermediate layer disposed in contact with the grain-oriented electrical steel sheet (silicon steel sheet) and an insulating coating disposed in contact with the intermediate layer.

[0170] For example, the above-mentioned intermediate layer may be a layer mainly composed of oxides, a layer mainly composed of carbides, a layer mainly composed of nitrides, a layer mainly composed of borides, a layer mainly composed of silicides, a layer mainly composed of phosphides, a layer mainly composed of sulfides, or a layer mainly composed of intermetallic compounds. These intermediate layers are formed primarily to ensure adhesion between the silicon steel sheet and the insulating coating, and may be known to be formed by heat treatment in an atmosphere with controlled oxidation-reduction properties, chemical vapor deposition (CVD), physical vapor deposition (PVD), etc.

[0171] Furthermore, typical examples of the above-mentioned insulating coatings include those mainly composed of phosphate and colloidal silica with an average thickness of 0.1 to 10 μm, and those mainly composed of alumina sol and boric acid with an average thickness of 0.5 to 8 μm. [Examples]

[0172] Next, the effects of the present invention will be specifically described in detail with reference to examples. The conditions in the examples are just one example of conditions adopted to confirm the feasibility and effects of the present invention, and the present invention is not limited to this one example of conditions. The present invention can adopt various conditions as long as they do not depart from the spirit of the invention and achieve the objectives of the present invention.

[0173] Decarburized annealed steel sheets were manufactured using slabs with the chemical compositions shown in Tables 1 and 2. The chemical composition of the manufactured decarburized annealed steel sheets was equivalent to that of the slabs shown in Tables 1 and 2, except for C (carbon). The C content of the manufactured decarburized annealed steel sheets is shown in Tables 17 to 23. These chemical compositions were measured based on the method described above. In Tables 1 and 2, "-" indicates that the content was not controlled or measured during manufacturing.

[0174] Furthermore, the decarburized annealed steel sheets described above were manufactured based on the manufacturing conditions shown in Tables 3 to 16. Slab heating was performed by soaking at a predetermined temperature for a predetermined time without temporarily increasing the heating temperature during the slab heating process. In the tables, the soaking temperature represents the surface temperature of the slab after heating, and the soaking time represents the slab heating time from the time the slab surface temperature reached the soaking temperature.

[0175] Although not shown in the table, when the total content of Nb group elements is 0.0030 to 0.030 mass%, by setting the slab soaking temperature to over 1030°C and less than 1180°C, and the slab soaking time to over 70 minutes, 12 to 85 volume percent of precipitates are dissolved, based on the precipitates contained in the slab after the casting process.

[0176] Using the manufactured decarburized annealed steel sheets, the average particle size and the particle size-detection intensity distribution of precipitates were investigated based on the method described above. The measurement results are shown in Tables 17-23. Note that in the tables, Dp Al This represents the most frequent diameter of Al-based precipitates, and Dp Nb This represents the most frequent diameter of Nb-based precipitates.

[0177] Furthermore, the manufactured decarburized annealed steel sheets were subjected to nitriding treatment (nitriding annealing) in a mixed atmosphere of hydrogen, nitrogen, and ammonia.

[0178] Furthermore, an annealing separation agent mainly composed of MgO was applied to the steel plate, and finish annealing was performed. In the final stage of finish annealing, the steel plate was held at 1200°C in a hydrogen atmosphere for 20 hours (purification annealing) and then allowed to cool naturally.

[0179] A coating solution for forming an insulating film, mainly composed of phosphate and colloidal silica and containing chromium, was applied to the primary film (intermediate layer) formed on the surface of the manufactured grain-oriented electrical steel sheet (finish annealed steel sheet). The sheet was then heated and held in an atmosphere of hydrogen:nitrogen at 75% by volume:25% by volume, and then cooled to form an insulating film.

[0180] The manufactured grain-oriented electrical steel sheet, when viewed from a cross-section parallel to the thickness direction, had an intermediate layer placed in contact with the grain-oriented electrical steel sheet (silicon steel sheet) and an insulating coating placed in contact with this intermediate layer. The intermediate layer was a forsterite coating with an average thickness of 2 μm, and the insulating coating was an insulating coating mainly composed of phosphate and colloidal silica with an average thickness of 1 μm.

[0181] The obtained grain-oriented electrical steel sheets were evaluated for various properties. The evaluation results are shown in Tables 17-23.

[0182] (1) Magnetic properties of grain-oriented electrical steel sheets The magnetic properties of the grain-oriented electrical steel sheets were measured based on the Single Sheet Tester (SST) method specified in JIS C 2556:2015.

[0183] As a measure of magnetic properties, the magnetic flux density B8(T) in the rolling direction of the steel sheet was measured when excited at 800 A / m. A magnetic flux density B8 of 1.930 T or higher was considered acceptable. For reference, iron loss W, defined as power loss per unit weight (1 kg) of the steel sheet, was also measured under the conditions of AC frequency: 50 Hz and excitation magnetic flux density: 1.7 T. 17 / 50 (W / kg) was measured.

[0184] Of Nos. 1 to 111, the present invention examples showed favorable control of the average particle size of the decarburized annealed steel sheet and the particle size-detection intensity distribution of the precipitates contained in the decarburized annealed steel sheet, and all exhibited excellent magnetic flux density as grain-oriented electrical steel sheets. On the other hand, of Nos. 1 to 111, the comparative examples did not show favorable control of the average particle size of the decarburized annealed steel sheet or the particle size-detection intensity distribution of the precipitates contained in the decarburized annealed steel sheet, and thus could not obtain a favorable magnetic flux density as grain-oriented electrical steel sheets.

[0185] [Table 1]

[0186] [Table 2]

[0187] [Table 3]

[0188] [Table 4]

[0189] [Table 5]

[0190] [Table 6]

[0191] [Table 7]

[0192] [Table 8]

[0193] Table 9

[0194] Table 10

[0195] Table 11

[0196] Table 12

[0197] Table 13

[0198] Table 14

[0199] Table 15

[0200] Table 16

[0201] Table 17

[0202] Table 18

[0203] Table 19

[0204] [Table 20]

[0205] [Table 21]

[0206] [Table 22]

[0207] [Table 23] [Industrial applicability]

[0208] According to the above aspects of the present invention, it is possible to provide a decarburized annealed steel sheet for grain-oriented electrical steel sheets that can increase magnetic flux density, thus having high industrial applicability.

Claims

[Claim 1] In decarburized annealed steel sheets for grain-oriented electrical steel sheets, The decarburized annealed steel sheet is, by mass%, C: 0-0.10%, Si: 2.0 to 7.0%, Mn: 0.050 to 1.0%, S: 0-0.0350%, Se: 0 to 0.0350%, S+Se total content: 0.0030-0.0350%, Al: 0.010-0.0650%, N: 0.0040-0.0120%, Nb: 0 to 0.030%, V: 0 to 0.030%, Mo: 0 to 0.030%, Ta: 0 to 0.030%, W: 0-0.030%, Nb + V + Mo + Ta + W total content: 0.0030 to 0.030%, Cu: 0 to 0.40%, Bi: 0 to 0.010%, B: 0 to 0.080%, P: 0-0.50%, Ti: 0 to 0.0150%, Sn: 0 to 0.10%, Sb: 0 to 0.10%, Cr: 0 to 0.30%, Ni: 0-1.0%, It contains and has a chemical composition consisting of Fe and impurities as the remainder, The precipitate, which is the residue obtained by electrolytic extraction of the decarburized annealed steel sheet, was analyzed by measuring the particle size-detection intensity distribution based on a calibration curve created from six types of standard particles with particle sizes of 29 nm, 48 nm, 100 nm, 200 nm, 300 nm, and 500 nm. The most frequent diameter of Al-based precipitates in nanometers (Dp) Ａｌ year, The most frequent diameter of Nb precipitates in units of nm (Dp) Ｎｂ In that case, Dp Ｎｂ 45-250 nm, Dp Ａｌ -Dp Ｎｂ 10-50 nm, Satisfying the conditions, The average particle size of the decarburized annealed steel sheet is 13 to 19 μm. A decarburized annealed steel sheet for grain-oriented electrical steel sheets, characterized by the following features.

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