WO2021045212A1 - 方向性電磁鋼板およびその製造方法 - Google Patents
方向性電磁鋼板およびその製造方法 Download PDFInfo
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- WO2021045212A1 WO2021045212A1 PCT/JP2020/033662 JP2020033662W WO2021045212A1 WO 2021045212 A1 WO2021045212 A1 WO 2021045212A1 JP 2020033662 W JP2020033662 W JP 2020033662W WO 2021045212 A1 WO2021045212 A1 WO 2021045212A1
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 77
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- 230000000694 effects Effects 0.000 description 11
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- 238000005097 cold rolling Methods 0.000 description 7
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 7
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
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- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
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- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/02—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling heavy work, e.g. ingots, slabs, blooms, or billets, in which the cross-sectional form is unimportant ; Rolling combined with forging or pressing
- B21B2001/028—Slabs
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/05—Grain orientation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a grain-oriented electrical steel sheet having stable magnetic properties and excellent iron loss characteristics, and a method for manufacturing the same.
- Electrical steel sheet is a material mainly used for iron cores such as transformers.
- iron cores such as transformers.
- the grain-oriented electrical steel sheet which is the material of the iron core, is also required to have better magnetic properties, that is, low iron loss and high magnetic flux density.
- the grain-oriented electrical steel sheet has a crystal structure in which the ⁇ 001> orientation, which is the axis for easily magnetizing iron, is highly aligned in the rolling direction of the steel sheet.
- Such an texture preferentially grows the crystal grains in the ⁇ 110 ⁇ ⁇ 001> orientation, which is the so-called Goss orientation, during the manufacturing process of the directional electromagnetic steel plate, especially during finish annealing. Formed through secondary recrystallization. Therefore, the crystal orientation of the secondary recrystallized grains has a great influence on the magnetic properties of the grain-oriented electrical steel sheet.
- Such grain-oriented electrical steel sheets are manufactured by the following steps. That is, a steel slab containing Si in an amount of about 4.5% by mass or less and further containing an element forming an inhibitor such as MnS, MnSe, AlN and BN is heated to 1300 ° C. or higher, hot-rolled, and if necessary. After hot-rolled sheet annealing, the final sheet thickness is obtained by cold rolling once or two or more times with intermediate annealing in between, and then primary recrystallization and decarburization are performed by primary recrystallization annealing in a moist hydrogen atmosphere. Further, it has been manufactured by applying an annealing separator containing magnesia as a main component and then performing finish annealing at 1200 ° C. for about 5 hours for secondary recrystallization and purification of inhibitor-forming elements (for example, patent). Documents 1, 2, 3, etc.).
- Patent Document 4 a method capable of expressing secondary recrystallization without containing an inhibitor-forming element, a so-called inhibitorless method, has been developed (for example, Patent Document 4).
- This method is completely different from the conventional method for manufacturing grain-oriented electrical steel sheets. That is, in the conventional method, secondary recrystallization was expressed using precipitates (inhibitors) such as MnS, MnSe, and AlN, but in the inhibitorless method, these inhibitors are not used, but rather the purity is increased. By reducing the resistance to grain boundary movement, the original difference in grain boundary movement speed depending on the grain boundary character is clarified, and the desired secondary recrystallization has been successfully expressed.
- precipitates inhibitors
- Patent Document 5 has proposed a technique for obtaining stable magnetic properties by reducing oxides containing Ca and / or Mg having a diameter of 1 to 3 ⁇ m. As a result, stable magnetic characteristics can be obtained over the entire length of the coil.
- the magnetic properties may not be stable due to the strong influence of the thermal history of annealing in the intermediate process. ..
- the present invention advantageously solves the above problems, and an object of the present invention is to obtain a grain-oriented electrical steel sheet which is stable over the entire length of the coil and has excellent magnetic characteristics.
- the inventors evaluated the characteristics of the material with a large "fluctuation allowance" of the magnetic characteristics in the coil, which occurs frequently, by various methods, and proceeded with a diligent investigation to clarify the characteristics.
- the characteristics of the product with a large "fluctuation allowance” of the characteristics are that the acid-soluble Ti is less than 5 ppm or more than 25 ppm among the Ti contained in the steel, and the particle size containing Ti and N is 200 nm or more. It was found that the number of precipitates to be obtained was less than 0.05 pieces / mm 2.
- Ti existence form it was recognized that in the product coil, particles having a particle size of 200 nm or more were present together with N, and the presence frequency was less than 0.05 / mm 2 and the magnetic fluctuation was large. .. Precipitates commonly used as inhibitors have a particle size of less than 100 nm. If the particle size is 200 nm or more, the density is inevitably low, and the function as an inhibitor is low.
- Ti forms oxides (TiO 2 ) and nitrides (TiN), but since oxides do not dissolve in acids, it is considered that acid-soluble Ti evaluates what exists as nitrides. ..
- N is detected together with Ti in the particles recognized by observation, and they exist in the form of TiN.
- TiN is known to act as a precipitation site for sulfides such as MnS.
- sulfides such as MnS.
- nitrides such as AlN.
- the observed particles were observed with sulfides, nitrides, and oxides of Si and Al, as shown in FIGS. 1A and 1B, and were in the form of composite precipitation. From these observation results, the reason why the variation in the final magnetic properties is suppressed is that when an appropriate amount of Ti is present in an appropriate size as a nitrogen-containing precipitate, it functions as a complex precipitation site and is inhibitorless. It was found that it may promote the purification that is important in the system.
- the inventors further examined such findings and completed the present invention.
- the gist structure of the present invention is as follows. 1. 1. In mass%, C: 0.005% or less, Si: 2.0 to 4.5% and Mn: 0.01 to 0.5%, and in mass ppm, N is 20 ppm or less, Se, Te and O are less than 50 ppm, and S is less than 30 ppm.
- acid-soluble Al less than 40 ppm, Ti less than 30 ppm, acid-soluble Ti of the Ti is 5 ppm or more and 25 ppm or less, the rest has the component composition of Fe and unavoidable impurities, and Ti A directional electromagnetic steel plate containing 0.05 particles / mm 2 or more of precipitates having a particle size of 200 nm or more containing and N.
- composition of the components is further mass%, Ni: 1.50% or less, Sn: 0.50% or less, Sb: 0.50% or less, Cu: 0.50% or less, Mo: 0.50% or less, P: 0.50% or less, Cr: 1.50%.
- a steel slab cast from molten steel having an impurity composition is hot-rolled to obtain a hot-rolled plate, then annealed and rolled to obtain a cold-rolled plate with a final plate thickness, and then primary recrystallization annealing is performed.
- a steel slab cast from molten steel having the composition of the above is subjected to hot rolling to obtain a hot-rolled plate, which has a step of first reducing the pressure and then holding the steel slab at a temperature of 1000 ° C. or higher for 40 seconds or longer.
- ferroalloy containing Si To adjust the composition of the molten steel, add the ferroalloy containing Si, the ferroalloy containing Al, and the ferroalloy containing Ti, add the ferroalloy containing Si, and then add the ferroalloy containing Al. Prior to the addition, 50% or more of the total amount of the ferroalloy containing the Ti is added in this order so that at least the Ti in the molten steel is less than 50 ppm, and then the acid-soluble Ti among the Ti is 5 ppm.
- a hot-rolled steel sheet for manufacturing grain-oriented electrical steel sheets which contains less than 50 ppm of Ti and has an acid-soluble Ti of 5 ppm or more and 30 ppm or less among the Tis.
- C 0.08% or less C has the function of suppressing grain coarsening during hot rolling and improving the pre-cold rolling structure, and in cold rolling, after primary recrystallization due to interaction with dislocations. Improve the collective organization of. However, if it remains on the final product plate, it causes magnetic aging and causes magnetic deterioration.
- the load becomes high in the intermediate decarburization process and cannot be sufficiently reduced, so the content is limited to 0.08% or less. Further, in order to obtain the above-mentioned tissue improvement effect, it is desirable that the lower limit is 0.01%.
- Si 2.0-4.5% Si is a useful element that improves iron loss by increasing electrical resistance. If the content is less than 2.0%, a sufficient iron loss reduction effect cannot be expected, while if it exceeds 4.5%, cold rolling becomes extremely difficult, so the Si content was limited to the range of 2.0% or more and 4.5% or less. Preferably, it is 2.0% or more and 4.0% or less.
- Mn 0.01-0.5% Mn is a useful element that improves hot workability, but if it is contained in excess of 0.5%, the primary recrystallization texture deteriorates and it is difficult to obtain secondary recrystallized grains that are highly integrated in the Goss orientation. Therefore, it was limited to the range of 0.5% or less. Further, in order to improve the hot workability, it is necessary to contain 0.01% or more. Preferably, it is 0.03% or more and 0.15% or less.
- Se, Te and O are less than 50 ppm, respectively. Excessive presence of Se and Te forms Se and Te compounds, which makes secondary recrystallization difficult. The reason for this is that the precipitate coarsened by slab heating makes the primary recrystallization structure non-uniform. Therefore, Se and Te are each suppressed to less than 50 ppm so as not to act as an inhibitor.
- the preferred content is 30 ppm or less.
- O forms an oxide and remains as an inclusion until the final product, which deteriorates the magnetic characteristics, and therefore needs to be suppressed to less than 50 ppm.
- the content of these elements may be 0%.
- Acid-soluble Al 20 ppm or more and less than 100 ppm, S: less than 50 ppm, N: 80 ppm or less
- these precipitate-forming elements are not always necessary considering only secondary recrystallization.
- an appropriate amount of Al is contained, a dense Al 2 O 3 film can be formed on the surface during secondary recrystallization annealing, and the influence of nitriding etc. can be reduced from the annealed atmosphere. Therefore, it is 20 ppm or more and less than 100 ppm. Incorporate in the range.
- the upper limit is limited to the above-mentioned numerical values.
- the lower limit of the amount of S and N added is preferably 0%, but these are elements that are difficult to completely remove, and actually setting S to less than 10 ppm and N to less than 20 ppm increases the manufacturing cost. Greatly increase.
- the inhibitorless method is intended to produce high-quality grain-oriented electrical steel sheets at low cost, and the above values are defined as the lower limit from the viewpoint of reducing the burden during such production.
- the magnetic properties of a steel sheet coil can be stabilized by fixing the sulfides and nitrides formed by S and N with an appropriate amount of Ti and purifying them in a pseudo manner. it can.
- Ti at the stage of molten steel to be subjected to continuous casting, it is necessary to set the amount of Ti to less than 50 ppm and then set the acid-soluble Ti to 5 ppm or more and 30 ppm or less in the existing state of Ti.
- Ti in steel forms particles such as TiO 2 and Ti N. Excessive presence of inclusions and precipitates thus formed leads to deterioration of magnetic properties, especially history loss. Therefore, it is necessary to control the amount of Ti to less than 50 ppm. Then, the acid-soluble Ti that leads to TiN precipitation in the subsequent step is controlled in the range of 5 ppm or more and 30 ppm or less.
- the addition of ferroalloy containing Ti contains Si. It is preferable to add 50% or more of the total amount of ferroalloy after adding the ferroalloy to be added and before adding the ferroalloy containing Al. Since Ti is a strong deoxidizing element, if oxygen in the molten steel is added at a high stage, it will combine with oxygen to form TiO 2 and will not easily become acid-soluble Ti. Therefore, it is preferable to adopt the procedure of adding Si before adding the Ti source.
- Al is known as a deoxidizing element stronger than Ti. Therefore, oxygen in the molten steel after addition of Al is removed by Al in the form of Al 2 O 3 , and it is expected that most of the added Ti will be in the form of acid-soluble Ti, and the acid in the molten steel. Soluble Ti may exceed 30ppm. Therefore, when the composition is adjusted using inexpensive ferroalloy that has relatively low purity and contains Ti as an impurity, after adding the ferroalloy containing Si, the ferroalloy containing Ti with respect to an appropriate amount of dissolved oxygen. Is added in an amount of 50% or more of the total addition amount, and after the acid-soluble Ti is analyzed after the addition, the ferroalloy containing Al is added.
- Ni 0.005 to 1.50%
- Ni has the function of improving the magnetic properties by increasing the uniformity of the hot-rolled plate structure. However, if the content is less than 0.005%, the effect of addition is poor, while if it exceeds 1.50%, secondary recrystallization becomes unstable and the magnetic properties deteriorate. Therefore, Ni should be contained in the range of 0.005 to 1.50%. Is desirable.
- Sn 0.01 to 0.50%
- Sb 0.005 to 0.50%
- Cu 0.01 to 0.50%
- the rest is iron and impurities other than those mentioned above, especially unavoidable impurities.
- the steel slab adjusted to the above-mentioned suitable composition range is subjected to hot rolling without reheating or after reheating.
- the reheating temperature is about 1100 ° C. or higher and 1300 ° C. or lower.
- heating the slab above 1300 ° C. is meaningless in the present invention in which the steel contains almost no inhibitor at the slab stage, and is unnecessary because it increases the cost.
- the first rolling it is preferable to hold the product at a temperature of 1000 ° C. or higher for 40 seconds or longer.
- a temperature of 1000 ° C. or higher for 40 seconds or longer.
- the upper limit of the holding time is not set in particular, it is desirable that the holding time is 600 seconds or less from the viewpoint of manufacturing. Further, from the viewpoint of securing 1000 ° C. after the first pass of hot rolling, it is desirable that the lower limit of the slab heating temperature is 1100 ° C. or higher.
- the particles containing Ti and N having an appropriate particle size formed through such a step hardly change in the post-step, and become pseudo sites for precipitation of sulfides and nitrides in the post-step. Demonstrates the effect of high purification. This effect is considered to be close to the effect used in the technology of trapping C in steel to make IF steel by adding Ti, for example.
- the hot-rolled plate is annealed with the hot-rolled plate as necessary, and then subjected to one cold rolling or two or more cold rollings sandwiching the intermediate annealing to obtain the final cold-rolled plate.
- This cold rolling may be performed at room temperature, or may be hot rolling in which the temperature of the steel sheet is raised to a temperature higher than room temperature, for example, about 250 ° C.
- the final cold rolled plate is subjected to primary recrystallization annealing.
- the purpose of this primary recrystallization annealing is to primary recrystallize a cold-rolled plate having a rolled structure and adjust it to the optimum primary recrystallization grain size for secondary recrystallization.
- the annealing atmosphere to an atmosphere of wet hydrogen nitrogen or wet hydrogen argon, carbon contained in the steel is decarburized, and at the same time, an oxide film is formed on the surface by the above annealing atmosphere. Therefore, it is desirable that the annealing temperature (retention temperature) of the primary recrystallization annealing is in the temperature range of 800 ° C. or higher and lower than 950 ° C.
- an annealing separator is applied to the surface of the steel sheet.
- Magnesia (MgO) is used as the main agent of the annealing separator in order to form a forsterite film on the surface of the steel sheet after the subsequent secondary recrystallization annealing.
- an auxiliary agent that uniformly promotes the formation of the forsterite film is also advantageous for improving the peeling characteristics.
- finish annealing is performed for secondary recrystallization and formation of a forsterite film.
- the annealing atmosphere of such finish annealing is suitable for N 2 , Ar, H 2 or a mixed gas thereof. Precipitation of trace components in the final product leads to deterioration of magnetic properties, so the maximum annealing temperature is preferably 1100 ° C or higher for component purification. Since the steel sheet of the present invention has little variation in magnetic characteristics in the coil, it is desirable to finish annealing with a coil having a mass of 5 tons or more, more preferably 10 tons or more in consideration of economic efficiency.
- an insulating film can be further applied and baked on the surface of the steel sheet.
- the type of the insulating coating is not particularly limited, and any conventionally known insulating coating is suitable.
- a coating solution containing phosphate-chromate-colloidal silica described in JP-A-50-79442 and JP-A-48-39338 is applied to a steel sheet and baked at about 800 ° C. The method is preferred.
- the components of the obtained final product are C: 0.005% or less, Si: 2.0 to 4.5%, Mn: 0.01 to 0.5% in the steel sheet base iron from which the insulating film and the base film have been removed as a result of purification by finish annealing.
- the grain-oriented electrical steel sheet of the present invention is further mass% Ni: 1.50% or less, Sn: 0.50% or less, Sb: 0.50% or less, Cu: 0.50% or less, Mo: It can contain one or more selected from 0.50% or less, P: 0.50% or less, Cr: 1.50% or less, B: 0.0050% or less, and Nb: 0.0100% or less.
- additive elements those having no lower limit are not particularly limited, and are allowed up to the lower limit of analysis including 0.
- other elements may be incorporated into the forsterite film or released into the gas phase depending on the finish annealing conditions, and the content in the steel may decrease. There are some that fall within the above range.
- Example 1 In addition to the main components, C: 0.06%, Si: 3.35% and Mn: 0.03%, slabs having various compositions shown in Table 1 were melted as other components. Se, Te and O were all 30 ppm. Ti was adjusted using a Ti ingot, and other component adjustments were made using high-purity ferroalloy containing almost no impurities such as Ti, or ingot or granular pure metal. Hot rolling was performed by heating the slab at 1250 ° C., after the first pass of hot rolling, and holding at 1000 ° C. or higher for 60 seconds to obtain a hot-rolled plate having a plate thickness of 2.5 mm.
- These hot-rolled plates were annealed at 900 ° C, cold-rolled to 1.3 mm, and then intermediate-annealed.
- the temperature was gradually changed from the tip of the coil to the tail end, and the temperature was 950 ° C at the tip of the coil and 1050 ° C at the tail end of the coil.
- the coil was cold-rolled to a final plate thickness of 0.23 mm and subjected to decarburization and annealing for primary recrystallization.
- an annealing separator containing MgO as a main component was applied, and final annealing including a secondary recrystallization process and a purification process was performed at a maximum temperature of 1150 ° C. and a soaking time of 10 hours.
- An insulating coat made of colloidal silica and magnesium phosphate was applied to the coil thus obtained and baked at 850 ° C. to obtain a product plate.
- the iron loss characteristics of each product board thus obtained were evaluated.
- the iron loss (W 17/50 ) is continuously measured over the entire length of each product plate coil, and the lowest value (lowest value), which is the best value, and the highest value (highest value), which is the worst value, are evaluated. did.
- samples were taken from the central part in the longitudinal direction and the central part in the width direction, and the Ti concentration was analyzed.
- a test piece for observing the L cross section was collected, 90 mm 2 was observed in a continuous field of view, and composition analysis was performed using EDX for all particles having a diameter equivalent to a circle and a diameter of 200 nm or more from the image of the particles.
- the number of particles containing both Ti and N elements was counted, and the value divided by the observation field area was obtained and used as the particle density in steel.
- the results are also shown in Table 1.
- the C, Si and Mn of the product board were all C: 0.001%, Si: 3.35% and Mn: 0.03%.
- Se, Te and O were all 30 ppm. According to the table, it can be seen that by following the present invention, the variation in magnetic characteristics is reduced and good characteristics are maintained.
- Target components are C: 0.05%, Si: 3.2%, Mn: 0.05%, Cr: 0.03%, P: 0.01%, acid-soluble Al: 30ppm, S: 20ppm, N: 30ppm, Se: 50ppm, Te: 30ppm.
- ferroalloys such as FeMn, FeCr, and FeP containing Ti as impurities are added after adding FeSi, and after analyzing Mn, Cr, P, and Ti, massive Al is added. After the addition, a small amount of the deficient portion was additionally added to produce slab A.
- the temperature is gradually changed from the tip of the coil to the tail end, the coil tip is 1000 ° C, the coil longitudinal center is 1025 ° C, and the coil tail end is. Annealed to 1050 ° C.
- the coil was cold-rolled to a final plate thickness of 0.27 mm and subjected to decarburization and annealing for primary recrystallization.
- an annealing separator containing MgO as a main component was applied, and the final annealing including the secondary recrystallization process and the purification process was carried out at a maximum temperature of 1200 ° C. and a soaking time of 10 hours.
- the obtained coil was coated with an insulating coating consisting of 60% colloidal silica and aluminum phosphate, and baked at 800 ° C.
- Epstein test pieces were cut out from the positions of the tip, center, and tail of the coil, iron loss (W 17/50 ) was measured, and the average value was calculated.
- the average value of the iron loss measurement results is shown in Table 2 in correspondence with the temperature at the time of annealing the hot-rolled plate.
- the C, Si and Mn of the product board were all C: 0.001%, Si: 3.2% and Mn: 0.05%.
- the Se, Te and O of the product board were Se: 10 ppm, Te: 5 ppm and O: 20 ppm, respectively.
- composition analysis by EDX is performed on all particles having a diameter equivalent to a circle and a diameter of 200 nm or more from the image of the particles, the number of particles containing both Ti and N elements is counted, and the observation field area is observed.
- the particle density in steel was calculated by dividing by.
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Abstract
Description
すなわち、Siを4.5質量%程度以下含有し、さらにMnS、MnSe、AlNおよびBNなどのインヒビターを形成する元素を含有する鋼スラブを、1300℃以上に加熱後、熱間圧延し、必要に応じて熱延板焼鈍を施し、その後、1回または中間焼鈍を挟む2回以上の冷間圧延によって最終板厚とし、ついで湿潤水素雰囲気で一次再結晶焼鈍することにより、一次再結晶および脱炭を行い、さらにマグネシアを主剤とする焼鈍分離剤を塗布してから、二次再結晶およびインヒビター形成元素の純化のために1200℃で5時間程度の仕上焼鈍を施すことにより製造されてきた(例えば、特許文献1、2、3など)。
この問題に対し、インヒビター形成元素を含有させなくとも二次再結晶を発現させることができる方法、いわゆるインヒビターレス法が開発された(例えば、特許文献4)。
その結果、特性の「変動代」の大きい製品の特徴として、鋼中の含有Tiのなかでも酸可溶性Tiが5ppm未満、あるいは25ppmを超えていること、またTiとNを含有する粒径200nm以上となる析出物が0.05個/mm2未満であることを見出した。なお、鋼中の析出物の評価は、製品コイルの幅、長手方向の中央位置からサンプルを切り出し、圧延方向(L方向)断面を連続した視野で90mm2の範囲を観察し、粒子の反射電子像から円相当径で直径が200nm以上となる粒子の全てに対して、EDXによる組成分析を行い、TiとNの両方を併せて含有する粒子数をカウントし、観察視野の面積で除した値で行った。
上記した今回の知見においても、最終製品コイルにおいて、酸可溶性Tiが25ppmを超える場合に磁性変動が大きかったのは、TiNがインヒビターとして機能し、不均一な組織を形成したことが原因と考えられる。一方で、磁気特性変動の大きくなるコイルの特徴として、酸可溶性Ti<5ppmという範囲が認められたことから、一定量の酸可溶性Tiは磁性安定化に寄与することを示しているものと考えられる。かかる知見は、酸可溶性Tiを適正に制御せず、不純物として混入されるに任せた製造を行った場合、特定の頻度で磁気特性の不安定化が生じる可能性があることを示唆している。
こうした観察結果から、最終的な磁気特性のバラつきが抑制される原因としては、適量のTiが窒素を含有する析出物として適正なサイズで存在する場合に、複合析出のサイトとして機能し、インヒビターレス系で重要な高純度化を促進している可能性があることを知見した。
1.質量%で、C:0.005%以下、Si:2.0~4.5%およびMn:0.01~0.5%を含み、並びに質量ppmで、Nを20ppm以下、Se、TeおよびOをそれぞれ50ppm未満、Sを30ppm未満および酸可溶性Alを40ppm未満含有し、さらにTiを30ppm未満含有すると共に、該Tiのうち酸可溶性Tiを5ppm以上25ppm以下とし、残部はFeおよび不可避的不純物の成分組成を有し、さらに、TiとNを含有する粒径200nm以上の析出物を0.05個/mm2以上で有する方向性電磁鋼板。
前記溶鋼の段階において、前記溶鋼中のTiを50ppm未満としたうえで、該Tiのうち酸可溶性Tiを5ppm以上30ppm以下とする方向性電磁鋼板の製造方法。
前記溶鋼の成分調整は、Siを含有する合金鉄、Alを含有する合金鉄およびTiを含有する合金鉄の添加を、前記Siを含有する合金鉄を添加後、前記Alを含有する合金鉄の添加前に、前記Tiを含有する合金鉄の全体量のうち50%以上を添加する順で行って、少なくとも前記溶鋼中のTiを50ppm未満としたうえで、該Tiのうち酸可溶性Tiを5ppm以上30ppm以下とする方向性電磁鋼板の製造方法。
まず、方向性電磁鋼板を製造する際の出発材となる、鋼スラブの成分組成の限定理由について述べる。なお、以下、成分に関する「%」および「ppm」表示は特に断らない限り質量%および質量ppmを意味するものとする。
C:0.08%以下
Cは、熱間圧延時の結晶粒粗大化を抑制し、冷延前組織を改善する機能を有し、また冷間圧延においては、転位との相互作用により一次再結晶後の集合組織を改善する。しかし、最終製品板に残留すると磁気時効の原因となり、磁性劣化を生じさせる。スラブ段階で0.08%を超えて含有させた場合、途中脱炭工程において負荷が高くなり、十分に低減できないため、0.08%以下に限定する。また上述の組織改善効果を得るためには、下限は0.01%であることが望ましい。
Siは、電気抵抗を高めることによって鉄損を改善する有用な元素である。含有量が 2.0%に満たないと十分な鉄損低減効果が望めず、一方4.5%を超えると冷間圧延が著しく困難になるため、Si量は2.0%以上4.5%以下の範囲に限定した。好ましくは、2.0%以上であり、4.0%以下である。
Mnは、熱間加工性を向上させる有用な元素であるが、0.5%を超えて含有した場合、一次再結晶集合組織が劣化し、Goss方位に高度に集積した二次再結晶粒が得難くなるので0.5%以下の範囲に限定した。また、熱間加工性を改善するためには、0.01%以上含有させる必要がある。好ましくは、0.03%以上であり、0.15%以下である。
SeおよびTeが過剰に存在するとSe化物、Te化物を形成し二次再結晶が困難となる。この理由は、スラブ加熱によって粗大化した析出物が一次再結晶組織を不均一にするためである。従って、インヒビターとして作用しないよう、Se、Teはそれぞれ50ppm未満に抑制する。好ましい含有量は30ppm以下である。また、Oは酸化物を作り、介在物として最終製品まで残留し、磁気特性を劣化させるため、50ppm未満に抑制する必要がある。なお、これらの元素の含有量は0%でもよい。
インヒビターレス法を適用する場合、これらの析出物形成元素は、二次再結晶のことだけを考えると必ずしも必要ではない。しかし、Alは、適量含有させることで二次再結晶焼鈍時、表面に緻密なAl2O3膜を形成し、焼鈍雰囲気から窒化等の影響を低減することができるため、20ppm以上100ppm未満の範囲で含有させる。
また、S、Nをそれぞれ50ppm以上、80ppm超含有した場合、SeやTe同様、スラブ加熱時に形成された析出物が粗大化し、一次再結晶組織を劣化させる。そのため、上限を上記した数値に限定する。
SやNの添加量の下限は好ましくは0%であるが、これらは完全に除去することは困難な元素であり、実際にSを10ppm未満、Nを20ppm未満とすることは、製造コストを大幅に高める。インヒビターレス法は低コストで良質な方向性電磁鋼板を製造しようとするものであり、こうした製造時の負担軽減の観点から上記の値を下限として規定した。
本発明は、こうしたSやNが形成する硫化物、窒化物を適正な量のTiによって固定し、疑似的に高純度化させることを以って、鋼板コイルの磁気特性を安定化させることができる。
鋼中のTiはTiO2、TiNといった粒子を形成する。こうして形成された介在物、析出物は過剰に存在すると、磁気特性、特に履歴損の劣化につながる。そのため、Ti量は50ppm未満に制御しておく必要がある。そのうえで、後工程でのTiN析出につながる酸可溶性Tiを、5ppm以上30ppm以下の範囲で制御する。不純物としてTiを含有しない純度の高い合金鉄を素材原料に利用する場合は、別途Ti源となる合金元素を添加する必要がある。そこで、製造コストを低減するために、本発明では、純度の低い合金鉄を積極的に利用することでTi量を高める手段をとることができる。
かかる手順を採用することにより、溶鋼中の酸素はSiO2の形である程度スラグ中に浮上し、鋼中から除去される。これによりTiの歩留りは上昇し、適度な範囲で酸可溶性Tiを高めることができる。
よって、比較的純度が低く、不純物としてTiを含有する安価な合金鉄を利用して成分調整を行う場合において、Siを含有する合金鉄を添加後、適度な溶存酸素に対してTi含有合金鉄を総添加量の50%以上で添加し、その添加後の酸可溶性Tiの分析を行ったうえで、Alを含有する合金鉄を添加する。その後、よりTi歩留りが高い状態でTi含有合金鉄の残りを添加し、適正範囲に制御する手法をとることができる。かかる手法をとれば、特に純度の高い合金鉄を利用することなく、適正範囲にTiを制御することが可能となる。もちろん、純度の高い合金鉄による成分調整を行うのであれば、このような手法は必ずしも必要ではない。
Ni:0.005~1.50%
Niは、熱延板組織の均一性を高めることにより、磁気特性を改善する働きがある。しかしながら、含有量が0.005%に満たないとその添加効果に乏しく、一方1.50%を超えると二次再結晶が不安定となり、磁気特性が劣化するので、Niは0.005~1.50%の範囲で含有させることが望ましい。
これらの元素は粒界偏析を介して補助インヒビターと見なされることもある元素であるが、析出物によるインヒビターを積極的に利用しないインヒビターレス法においては、有用に働く場合がある。それぞれ下限未満では添加効果に乏しく、一方上限を超えると二次再結晶不良の可能性が高まる。
これらの元素はフォルステライト被膜形成時、その反応を良好にする効果を有する。それぞれ下限未満では添加効果に乏しく、一方上限を超えると逆にフォルステライト被膜の形成が促進されすぎる結果、被膜が剥離してしまうなどの問題が生じる。
これらの元素はいずれも、粒成長の抑制に寄与し、集合組織改善効果と二次再結晶安定化の効果を有する。かかる効果を効率的に得るためには、それぞれ上記の範囲で含有させることが好ましい。過剰に添加すると、鋼中に析出して強いインヒビターとして機能するため、インヒビターレス法においては、上記の上限を超える含有は好ましくない。
本発明の鋼板はコイル内の磁気特性変動が少ないので、経済性を考慮して5トン以上、より好ましくは10トン以上の質量のコイルで仕上焼鈍することが望ましい。
なお、上記添加元素のうち下限の定めのないものは特に制限がないものであり、0を含む分析下限値以下まで許容する。また、それ以外の元素は、仕上げ焼鈍条件によって、フォルステライト被膜中に取り込まれたり、気相に放出されたりして、鋼中の含有量は低下する場合があるため、スラブ含有時の濃度以下となるものがあり、それぞれ上記の範囲となる。
主成分、C:0.06%、Si:3.35%およびMn:0.03%に加え、それ以外の成分として表1に示す種々の組成のスラブを溶製した。なお、Se、TeおよびOは、いずれも30ppmであった。Tiの調整はTi塊を用いて行い、他の成分調整はTi等の不純物をほとんど含有しない高純度合金鉄あるいは、塊状、粒状純金属を用いた。熱間圧延を1250℃のスラブ加熱後、熱間圧延初パス後、1000℃以上で60秒保持する条件で行い、板厚2.5mmの熱延板とした。
同表によれば、本発明に従うことによって、磁気特性のバラつきが低減し、かつ良好な特性を保っていることが分かる。
目標成分を、C:0.05%、Si:3.2%、Mn:0.05%、Cr:0.03%、P:0.01%、酸可溶性Al:30ppm、S:20ppm、N:30ppm、Se:50ppm、Te:30ppmおよびO:20ppmとする鋼を溶製する際、Tiを不純物として含有するFeMn、FeCr、FePといった合金鉄をFeSi添加後に添加し、Mn、Cr、P、Tiを分析した上で、塊状Alを添加したのちに、少量不足していた分を追加添加しスラブAを製造した。また、比較として、FeSi添加前に合金鉄を添加し、塊状Al添加後、少量不足していた分を追加添加したスラブB、塊状Al添加後、全ての成分調整を行ったスラブCをそれぞれ2本ずつ作製した。さらに、スラブAの製造手順で表2に記載の組成のスラブD~Fをそれぞれ2本ずつ作製した。
その後、それぞれ1200℃にスラブ加熱を行い、熱間圧延初パス後、1000℃以上で60秒保持した熱間圧延条件1と、初パス後30秒の間に980℃まで温度が低下した熱間圧延条件2で、板厚2mmの熱延板をそれぞれ作製した。
また、鉄損測定を行ったエプスタイン試験片から被膜を除去したうえで成分分析を行い、L断面観察用の試験片を採取し、連続した視野で90mm2を観察した。かかる観察において、粒子の像から円相当径で直径が200nm以上となる粒子の全てに対して、EDXによる組成分析を行い、TiとNの両元素を含有する粒子数をカウントし、観察視野面積で除した値で鋼中粒子密度を算出した。
Claims (7)
- 質量%で、C:0.005%以下、Si:2.0~4.5%およびMn:0.01~0.5%を含み、並びに質量ppmで、Nを20ppm以下、Se、TeおよびOをそれぞれ50ppm未満、Sを30ppm未満および酸可溶性Alを40ppm未満含有し、さらにTiを30ppm未満含有すると共に、該Tiのうち酸可溶性Tiを5ppm以上25ppm以下とし、残部はFeおよび不可避的不純物の成分組成を有し、さらに、TiとNを含有する粒径200nm以上の析出物を0.05個/mm2以上で有する方向性電磁鋼板。
- 前記成分組成が、さらに質量%で、
Ni:1.50%以下、
Sn:0.50%以下、
Sb:0.50%以下、
Cu:0.50%以下、
Mo:0.50%以下、
P:0.50%以下、
Cr:1.50%以下、
B:0.0050%以下および
Nb:0.0100%以下
のうちから選んだ1種または2種以上を含有する請求項1に記載の方向性電磁鋼板。 - 請求項1に記載の方向性電磁鋼板を製造する方法であって、質量%で、C:0.08%以下、Si:2.0~4.5%およびMn:0.01~0.5%を含有すると共に、質量ppmで、Tiを50ppm未満、Se、TeおよびOをそれぞれ50 ppm未満に抑制し、Sを50ppm未満、酸可溶性Alを20ppm以上100ppm未満に、さらにNを80ppm以下の範囲に制御し、残部はFeおよび不可避的不純物の成分組成を有する溶鋼から鋳造した鋼スラブに、熱間圧延を施して熱延板としたのち、焼鈍および圧延によって最終板厚の冷間圧延板とし、ついで一次再結晶焼鈍を行い、さらに二次再結晶焼鈍を施した後、絶縁被膜の形成を行う方向性電磁鋼板の製造方法であって、
前記溶鋼の段階において、前記溶鋼中のTiを50ppm未満としたうえで、該Tiのうち酸可溶性Tiを5ppm以上30ppm以下とする方向性電磁鋼板の製造方法。 - 請求項1に記載の方向性電磁鋼板を製造する方法であって、質量%で、C:0.08%以下、Si:2.0~4.5%およびMn:0.01~0.5%を含有すると共に、質量ppmで、Tiを50ppm未満、Se、TeおよびOをそれぞれ50ppm未満に抑制し、Sを50ppm未満、酸可溶性Alを20ppm以上100ppm未満に、さらにNを80ppm以下の範囲に制御し、残部はFeおよび不可避的不純物の成分組成を有する溶鋼から鋳造した鋼スラブに、最初の圧下を行ったのち、1000℃以上の温度で40秒以上の時間保持する工程を有する、熱間圧延を施して熱延板とし、さらに焼鈍および圧延によって最終板厚の冷間圧延板とし、ついで一次再結晶焼鈍を行い、二次再結晶焼鈍後、絶縁被膜の形成を行う方向性電磁鋼板の製造方法であって、
前記溶鋼の成分調整は、Siを含有する合金鉄、Alを含有する合金鉄およびTiを含有する合金鉄の添加を、前記Siを含有する合金鉄を添加後、前記Alを含有する合金鉄の添加前に、前記Tiを含有する合金鉄の全体量のうち50%以上を添加する順で行って、少なくとも前記溶鋼中のTiを50ppm未満としたうえで、該Tiのうち酸可溶性Tiを5ppm以上30ppm以下とする方向性電磁鋼板の製造方法。 - 請求項2に記載の方向性電磁鋼板を製造する方法であって、
請求項3または4に記載の鋼スラブにさらに質量%で、
Ni:0.005~1.50%、
Sn:0.01~0.50%、
Sb:0.005~0.50%、
Cu:0.01~0.50%、
Mo:0.01~0.50%、
P:0.0050~0.50%、
Cr:0.01~1.50%、
B:0.0001~0.0050%および
Nb:0.0005~0.0100%、
のうちから選んだ1種または2種以上を含有する請求項3または4に記載の方向性電磁鋼板の製造方法。 - 方向性電磁鋼板製造用熱延鋼板であって、
Tiを50ppm未満含有し、かつ該Tiのうち酸可溶性Tiが5ppm以上30ppm以下である方向性電磁鋼板製造用熱延鋼板。 - 請求項6に記載の方向性電磁鋼板製造用熱延鋼板であって、さらに、
TiとNを含有する粒径200nm以上の析出物を0.05個/mm2以上で有する方向性電磁鋼板製造用熱延鋼板。
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EP20861748.0A EP4026921A4 (en) | 2019-09-06 | 2020-09-04 | CORNO-ORIENTED ELECTROMAGNETIC STEEL SHEET AND PROCESS FOR PRODUCTION THEREOF |
MX2022002590A MX2022002590A (es) | 2019-09-06 | 2020-09-04 | Lamina de acero electrico de grano orientado y metodo de produccion de la misma. |
BR112022003971A BR112022003971A2 (pt) | 2019-09-06 | 2020-09-04 | Chapa de aço elétrico de grãos orientados e método de produção da mesma, e chapa de aço laminada a quente para uso na produção de uma chapa de aço elétrico de grãos orientados |
CA3153363A CA3153363A1 (en) | 2019-09-06 | 2020-09-04 | Grain-oriented electrical steel sheet and method of producing same |
KR1020227010886A KR20220056226A (ko) | 2019-09-06 | 2020-09-04 | 방향성 전자 강판 및 그의 제조 방법 |
CN202080062277.0A CN114364821B (zh) | 2019-09-06 | 2020-09-04 | 方向性电磁钢板及其制造方法 |
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CN (1) | CN114364821B (ja) |
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- 2020-09-04 KR KR1020227010886A patent/KR20220056226A/ko not_active Application Discontinuation
- 2020-09-04 CA CA3153363A patent/CA3153363A1/en active Pending
- 2020-09-04 MX MX2022002590A patent/MX2022002590A/es unknown
- 2020-09-04 CN CN202080062277.0A patent/CN114364821B/zh active Active
- 2020-09-04 BR BR112022003971A patent/BR112022003971A2/pt unknown
- 2020-09-04 JP JP2021507876A patent/JP7160181B2/ja active Active
- 2020-09-04 US US17/753,482 patent/US20220333220A1/en active Pending
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EP4026921A1 (en) | 2022-07-13 |
KR20220056226A (ko) | 2022-05-04 |
JPWO2021045212A1 (ja) | 2021-11-25 |
CA3153363A1 (en) | 2021-03-11 |
BR112022003971A2 (pt) | 2022-05-24 |
CN114364821B (zh) | 2023-10-20 |
CN114364821A (zh) | 2022-04-15 |
JP7160181B2 (ja) | 2022-10-25 |
MX2022002590A (es) | 2022-03-25 |
EP4026921A4 (en) | 2023-11-01 |
US20220333220A1 (en) | 2022-10-20 |
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