EP4653556A1 - Method for manufacturing grain-oriented electromagnetic steel sheet - Google Patents

Method for manufacturing grain-oriented electromagnetic steel sheet

Info

Publication number
EP4653556A1
EP4653556A1 EP24744695.8A EP24744695A EP4653556A1 EP 4653556 A1 EP4653556 A1 EP 4653556A1 EP 24744695 A EP24744695 A EP 24744695A EP 4653556 A1 EP4653556 A1 EP 4653556A1
Authority
EP
European Patent Office
Prior art keywords
annealing step
steel sheet
temperature
final
temperature gradient
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24744695.8A
Other languages
German (de)
French (fr)
Inventor
Ryo Matsubara
Yoshiyuki Ushigami
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Corp
Original Assignee
Nippon Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Corp filed Critical Nippon Steel Corp
Publication of EP4653556A1 publication Critical patent/EP4653556A1/en
Pending legal-status Critical Current

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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
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/34—Methods of heating
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • 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
    • C21D3/00—Diffusion processes for extraction of non-metals; Furnaces therefor
    • C21D3/02—Extraction of non-metals
    • C21D3/04—Decarburising
    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the working steps
    • C21D8/1222—Hot rolling
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the working steps
    • C21D8/1233—Cold rolling
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the heat treatment
    • C21D8/1255—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the heat treatment
    • C21D8/1261—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the heat treatment following hot rolling
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1244—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties characterised by the heat treatment
    • C21D8/1272—Final recrystallisation annealing
    • 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
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1283—Application of a separating or insulating coating
    • 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
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
    • 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
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • 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
    • H01F1/14791—Fe-Si-Al based alloys, e.g. Sendust
    • 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
    • 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

Definitions

  • the present invention relates to a method of manufacturing a grain-oriented electrical steel sheet.
  • the grain-oriented electrical steel sheet (also referred to as grain-oriented silicon steel sheet) is a soft magnetic material, and is mainly used as an iron core material of a transformer. Therefore, the grain-oriented electrical steel sheet is required to have a small energy loss (low iron loss).
  • the magnetic flux density: B8 (magnetic flux density in a magnetic field of 800 A/m) is the most dominant factor of iron loss characteristics. It is known that the higher the value of the magnetic flux density: B8, the lower the iron loss, and the better the iron loss characteristics.
  • the iron core can be downsized as the value of the magnetic flux density: B8 becomes higher, which is advantageous in terms of the device configuration of the transformer and also advantageous in terms of the manufacturing cost of the transformer.
  • Patent Document 1 discloses a method of manufacturing a grain-oriented electrical steel sheet having a high magnetic flux density in which a silicon steel slab containing 0.015% or less of C, 4% or less of Si, 0.012% or less of S, 0.020 to 0.065% of acid-soluble Al, and 0.0030 to 0.0095% of T.N is heated at 1270°C or lower and then hot-worked into a hot rolled sheet, the hot rolled sheet is coiled at 700 to 950°C and then cold-rolled at a rolling reduction of 65% or more, the steel sheet is annealed for primary recrystallization for a short time, and then the steel sheet is subjected to final annealing at high temperature including treatment of growing secondary recrystallization grains while applying a temperature gradient of 2 °C/cm or more to the steel sheet in the boundary portion between the primary recrystallization region and the secondary recrystallization region.
  • Patent Document 2 discloses a method of manufacturing a grain-oriented silicon steel sheet having an ultra-low iron loss including achieving crystal orientation control through secondary recrystallization and a smooth steel sheet surface to manufacture a grain-oriented electrical steel sheet having an ultra-low iron loss at low cost also for a material having a thin sheet thickness (for example, 0.13 mm), which has been difficult to manufacture conventionally.
  • Patent Document 2 discloses that it is necessary to raise the temperature to 1000 to 1100°C at a temperature rising rate of 50 °C/hr or more in the final annealing in order to secure a temperature gradient of at least 2 °C/cm.
  • Patent Document 3 discloses a method of manufacturing a grain-oriented silicon steel sheet (band) having a high magnetic flux density in which secondary recrystallization proceeds while the steel sheet (band) is applied with a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region during the manufacturing process of a grain-oriented silicon steel sheet (band).
  • Patent Documents 4 and 5 disclose equipment and methods for imparting a temperature gradient to a coiled steel sheet.
  • the present inventors calculated the temperature gradient of each portion of a coil by simulation using a known heat transfer calculation software, Fluent (registered trademark), developed by ANSYS, and found that even when a temperature gradient of 2 °C/cm or more is applied, a region having a low-temperature gradient of about 0.5 °C/cm (small temperature gradient) exists in some parts of the coil. It was found that when a coil is applied with a temperature gradient, particularly to a large temperature gradient, the temperature gradient tends to be smaller inside the coil than outside the coil. That is, for example, even when the temperature gradient is 2 °C/cm or more outside the coil, there is a low-temperature gradient of less than 2 °C/cm in some regions inside the coil or the like.
  • Fluent registered trademark
  • the temperature gradient tends to be smaller on the low-temperature end than on the high-temperature end.
  • the temperature gradient is 2 °C/cm or more on the high-temperature end of the coil, there may be a low-temperature gradient of less than 2 °C/cm in some parts on the low-temperature end or the like. Therefore, it is difficult to apply a temperature gradient of 2 °C/cm or more throughout a coil.
  • Patent Document 3 discloses that an effect of improving B8 characteristics is recognized by imparting a temperature gradient of 0.5 °C/cm. However, Patent Document 3 indicates that a remarkable effect is obtained at 2 °C/cm or more. In fact, the B8 value of a grain-oriented electrical steel sheet having a Si content of 2.95% is about 1.92 T under a temperature gradient of 0.5 °C/cm, which means that a certain effect of improving the magnetic flux density is obtained, but it cannot be said to be sufficient for the recent advanced requirements.
  • An object of the present invention is to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method for manufacturing a grain-oriented electrical steel sheet stably having a high magnetic flux density throughout a coil by obtaining a sufficient effect of improving magnetic flux density even under a small temperature gradient.
  • the present inventors examined a method for obtaining a sufficient effect of improving the magnetic flux density even under a relatively small temperature gradient (even when the lower limit of the temperature gradient is small in a case where a large temperature gradient part and a small temperature gradient part are generated).
  • the present invention has been made in view of the above findings.
  • the gist of the present invention is as follows.
  • the present invention it is possible to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method of manufacturing a grain-oriented electrical steel sheet capable of obtaining a sufficient effect of improving magnetic flux density even under a small temperature gradient.
  • a silicon steel material such as a slab having a chemical composition described later is heated to a temperature of higher than 1300°C and hot rolling, to obtain a hot rolled sheet.
  • the heating temperature When the heating temperature is higher than 1300°C, the precipitate acting as an inhibitor completely becomes a solid solution, and is finely precipitated during the hot rolling and the subsequent annealing steps, so that grain growth is suppressed from the decarburization annealing step to the final annealing step.
  • the heating temperature may be 1310°C or higher, or may be 1350°C or higher.
  • the upper limit of the heating temperature is not limited. However, when the heating temperature is excessively increased, good magnetic characteristics may fail to be obtained due to insufficient secondary recrystallization. Therefore, the heating temperature is preferably 1450°C or lower.
  • the hot rolling conditions other than the heating temperature are not limited, and may be in a known range according to required characteristics and the like.
  • the silicon steel material to be subjected to hot rolling is obtained by smelting steel in a converter, an electric furnace, or the like, subjecting the molten steel to a vacuum degassing treatment as necessary, and then subjecting the molten steel to continuous casting or blooming after an ingot is made.
  • the silicon steel material contains 0.80 to 7.00% of Si in terms of mass%.
  • the silicon steel material includes, as the chemical composition, in terms of mass%, 0.80 to 7.00% of Si, 0.15% or less of C, 0.010 to 0.065% of acid-soluble Al, 0.004 to 0.012% of N, 0.01 to 0.50% of Mn, 0.01 to 0.05% in total of S and Se, 0 to 0.30% of Cr, 0 to 0.4% of Cu, 0 to 0.5% of P, 0 to 1.00% of Ni, and a balance of Fe and impurities.
  • the Si content is 0.80% or more.
  • the Si content is preferably 1.50% or more, more preferably 2.00% or more, and still more preferably 2.50% or more.
  • the Si content is more than 7.00%, it is extremely difficult to perform cold rolling, and there is a possibility of cracking during rolling. Therefore, the Si content is 7.00% or less.
  • the Si content may be 4.80% or less, or may be 4.00% or less.
  • the C is an effective element for controlling the primary recrystallization structure, but has an adverse effect on the magnetic characteristics. Therefore, it is necessary to perform decarburization before the final annealing.
  • the C content is more than 0.15% in the silicon steel material, the decarburization annealing time becomes long, and industrial productivity is impaired. Therefore, the C content is preferably 0.15% or less.
  • the C content is more preferably 0.12% or less.
  • the lower limit of the C content is not particularly limited, but is preferably 0.02% or more, more preferably 0.03% or more, and further preferably 0.05% or more in consideration of industrial productivity and magnetic properties of products.
  • Acid-soluble Al is an element that binds to N and functions as an inhibitor as AIN or (Al, Si)N.
  • the acid-soluble Al content is preferably 0.010 to 0.065%.
  • the acid-soluble Al content may be 0.040% or less, and further, may be 0.030% or less.
  • N is an element that binds to Al and functions as an inhibitor.
  • the N content is preferably 0.004% or more.
  • the N content is more preferably 0.006% or more, still more preferably 0.007% or more.
  • the N content is more than 0.012%, pores called blisters may be generated in the steel sheet during cold rolling. Therefore, the N content is preferably 0.012% or less.
  • the silicon steel material may contain, as the chemical composition, the above elements, and the balance may be Fe and impurities. On the other hand, in order to improve various properties, the following elements may be further contained.
  • Mn is an element that functions as an inhibitor as MnS or MnSe.
  • the Mn content is preferably 0.01% or more.
  • the Mn content is more preferably 0.03% or more, and still more preferably 0.06% or more.
  • the Mn content is more than 0.50%, it is difficult to make a solid solution of Mn during heating of the silicon steel material, which is not preferable.
  • the Mn content is more than 0.50%, the precipitation size of MnS and MnSe as an inhibitor tends to be coarsened, and the optimum size distribution as an inhibitor is impaired, which is not preferable. Therefore, the Mn content is preferably 0.50% or less.
  • the Mn content is more preferably 0.30% or less, and still more preferably 0.28% or less.
  • Mn is an element having an effect of increasing specific resistance and reducing iron loss. Mn is an effective element for preventing the occurrence of cracking in hot rolling caused by S or Se. In order to prevent the occurrence of cracking, the Mn content is preferably in a range satisfying Mn/(S + Se) ⁇ 4 in relation to the total amount of S and Se.
  • S and Se form an inhibitor together with Mn.
  • the total content of S and Se is preferably 0.01% or more.
  • the total content of S and Se is more preferably 0.02% or more.
  • the total content of S and Se exceeds 0.05%, hot embrittlement is caused, and hot rolling is significantly difficult. Therefore, the total content of S and Se is preferably 0.05% or less. The total content of S and Se is preferably 0.04% or less.
  • Cr is an element that brings the composition and amount of the oxide layer of the decarburization annealing into a preferable state and promotes the formation of a glass coating. Thus, Cr may be included.
  • the Cr content is more than 0.30%, decarburization is inhibited. Therefore, the Cr content is preferably 0.30% or less.
  • Cu is an effective element for increasing specific resistance and reducing iron loss. Thus, Cu may be included.
  • the Cu content is more than 0.4%, the iron loss reduction effect is saturated, and a surface defect called "copper scab" is caused during hot rolling. Therefore, the Cu content is preferably 0.4% or less.
  • P is an effective element for increasing specific resistance and reducing iron loss.
  • P may be included.
  • the P content is more than 0.5%, the rollability is deteriorated. Therefore, the P content is preferably 0.5% or less.
  • Ni is an effective element for increasing specific resistance and reducing iron loss.
  • Ni is an effective element for controlling the metallographic structure of the hot rolled sheet to improve magnetic characteristics.
  • Ni may be included.
  • the Ni content is preferably 1.00% or less.
  • Impurity refers to an element that is mixed from a raw material or in a manufacturing process and does not clearly affect the characteristics of the grain-oriented electrical steel sheet obtained by the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment.
  • the chemical composition of the silicon steel material may be measured by a known method.
  • the chemical composition may be measured using inductively coupled plasma-atomic emission spectrometry (ICP-AES).
  • ICP-AES inductively coupled plasma-atomic emission spectrometry
  • Al may be measured by ICP-AES using, as acid-soluble Al, a filtrate after a sample is thermally decomposed with an acid.
  • Si may be measured by the silicon dioxide weight method
  • C and S may be measured by the combustion-infrared absorption method
  • N may be measured by the inert gas fusion-thermal conductivity method.
  • O may be measured using the inert gas fusion-non-dispersive infrared absorption method.
  • the above chemical composition refers to the components of the silicon steel sheet as a base metal.
  • the grain-oriented electrical steel sheet as a measurement sample has a glass coating, an insulating coating, or the like on the surface, the chemical composition is measured after these coatings are removed by a known method.
  • the hot rolled sheet obtained by hot rolling is subjected to annealing (hot rolled sheet annealing) in order to enhance magnetic characteristics.
  • annealing condition may be, for example, a condition of holding at 900 to 1200°C for 30 seconds to 30 minutes.
  • the annealing temperature may be 950 to 1050°C.
  • the hot rolled sheet after the hot rolling step or after the hot-rolled sheet annealing step is subjected to cold rolling to obtain a steel sheet (cold rolled sheet) having a sheet thickness equal to the final sheet thickness (the sheet thickness of the completed grain-oriented electrical steel sheet (when a glass coating or an insulating coating is formed on the surface thereof, the sheet thickness of the base steel sheet excluding the coatings)).
  • the cold rolling may be performed one time (in series without intervening intermediate annealing) or two or more times with intervening annealing (intermediate annealing).
  • the final rolling reduction is preferably 80% or more.
  • the final rolling reduction is a cumulative rolling reduction of cold rolling, and when intermediate annealing is performed, the final rolling reduction is a cumulative rolling reduction of cold rolling after the final intermediate annealing.
  • the steel sheet after the cold rolling step is subjected to decarburization annealing.
  • the steel sheet In the decarburization annealing, the steel sheet is primarily-recrystallized and C, which adversely affects magnetic characteristics, is removed from the steel sheet.
  • the primary recrystallization grain size (the grain size of the primary recrystallization grain) is 15 ⁇ m or less.
  • the primary recrystallization grain size may be 13 ⁇ m or less, and further may be 10 ⁇ m or less.
  • the primary recrystallization grain size is 15 ⁇ m or less to enhance the driving force and the steel sheet has a nitrogen amount of 210 ppm (0.0210 mass%) or more based on mass through the nitriding treatment to thermally stabilize the inhibitor, it is possible to preferentially grow only ⁇ 110 ⁇ ⁇ 001> oriented grains having good magnetic characteristics even under a low-temperature gradient.
  • the heating temperature of the silicon steel material in the hot rolling step described above is higher than 1300°C, and then the annealing temperature and time may be controlled in the decarburization annealing step.
  • the annealing temperature in the decarburization annealing step is not limited, and may be, for example, 700°C or higher and 850°C or lower, and may be 750°C or higher, or 800°C or lower.
  • the holding time of the annealing temperature is not limited, and may be 10 to 600 seconds.
  • the primary recrystallization grain size after the decarburization annealing step is measured by the following method.
  • a sample is collected from the steel sheet after the decarburization annealing step and before the final annealing step, a cross section of the sample parallel to the rolling direction and parallel to the sheet thickness direction is observed with an optical microscope, the average grain size (circle equivalent diameter) of the primary recrystallization grains in the entire thickness of the cross section is determined by image analysis, and the average value is determined as the primary recrystallization grain size.
  • one visual field or more visual fields are observed, and 500 or more grains are observed.
  • the steel sheet after the decarburization annealing step is applied with an annealing separator, and then coiled into a coil shape.
  • the annealing separator to be applied may be a known one, but an annealing separator containing magnesia as a main component is preferable.
  • an annealing separator containing magnesia as a main component By applying an annealing separator containing magnesia as a main component and performing the subsequent final annealing, a glass coating (forsterite coating) is formed on the surface of the steel sheet.
  • the nitrogen amount in the steel sheet is increased.
  • the nitriding treatment step is performed at least in one stage of: during the decarburization annealing step; between the decarburization annealing step and the final annealing step; and after the start of the final annealing step and before the start of the secondary recrystallization in the temperature raising process in the final annealing step. Between the decarburization annealing step and the final annealing step means between the completion of the decarburization annealing step and the start of the final annealing step.
  • the nitriding treatment step is preferably performed after the completion of the decarburization annealing step and before the start of the annealing separator applying step.
  • the nitrogen amount in the steel sheet is required to be 210 ppm (0.0210 mass%) or more based on mass after the final nitriding treatment step.
  • the nitrogen amount may be 250 ppm or more, and further, may be 300 ppm or more.
  • the nitrogen amount is more than 350 ppm, the effect of improving the magnetic flux density may be saturated, and there is also a possibility that purification after secondary recrystallization will be disadvantageous. Therefore, the nitrogen amount is preferably 350 ppm or less.
  • JP S59-215419 A discloses that when secondary recrystallization annealing is performed while the boundary region between the primary recrystallization region and the secondary recrystallization region is applied with a temperature gradient in the final annealing, the nitrogen content in the steel sheet is 130 to 200 ppm at the start of secondary recrystallization. JP S59-215419 A describes that the magnetic flux density improving effect is saturated at a nitrogen content of 180 to 200 ppm.
  • the present inventors have found that when the primary recrystallization grain size is 15 ⁇ m or less and the nitrogen amount is increased to 210 ppm or more, the lower limit of the temperature gradient at which high magnetic flux density (for example, B8 is stably 1.940 T or more) can be achieved is expanded compared with the conventional case (high B8 is stably obtained even when the temperature gradient is about 0.5 °C/cm).
  • Examples of the method for increasing the nitrogen amount in the steel sheet include a method of annealing the steel sheet in an atmosphere containing a gas having nitriding ability to control the nitrogen amount in the steel sheet.
  • the nitrogen amount in the steel sheet may be increased by adding a powder having nitriding ability such as MnN to an annealing separator in the temperature raising process in the final annealing step.
  • the nitrogen amount in the steel sheet after the nitriding treatment can be measured by a known method using, for example, an oxygen-nitrogen-hydrogen analyzer (EMGA-930) manufactured by HORIBA, Ltd. or an apparatus equivalent thereto.
  • EMGA-930 oxygen-nitrogen-hydrogen analyzer
  • a general analysis method such as the inert gas fusion-thermal conductivity method can be used.
  • a sample having an arbitrary size may be collected from the steel sheet after the nitriding treatment step in the manufacturing process, and measured using these devices and methods.
  • the steel sheet coiled into a coil shape is subjected to final annealing.
  • the final annealing step includes: a temperature raising process of heating to a final annealing temperature for secondary recrystallization; and a soaking process of holding the steel sheet at the final annealing temperature.
  • a temperature gradient of 0.5 °C/cm or more is generated in a boundary region between a primary recrystallization region and a secondary recrystallization region at least in one period from the start of secondary recrystallization to completion of the secondary recrystallization in the temperature raising process, and ⁇ 110 ⁇ ⁇ 001> oriented grains are preferentially grown through secondary recrystallization. Even if a temperature gradient is applied at a time other than the above time, for example, before the final annealing, a similar effect cannot be obtained.
  • the temperature rising rate is not limited as long as the temperature gradient is satisfied, and may be 50 °C/h or less.
  • secondary recrystallized grains are generated in a portion heated to the secondary recrystallization temperature or higher.
  • secondary recrystallization proceeds from the region where the temperature is equal to or higher than the secondary recrystallization temperature; and between the above region and the region where the secondary recrystallization temperature has not been reached and the primary recrystallization structure still remains, a region where primary recrystallization grains and secondary recrystallization grains are mixed in the sheet thickness direction (boundary region) is generated along the isotherm.
  • this boundary region moves along the temperature gradient to the region where the primary recrystallization structure remains, so that the region that has become the secondary recrystallization structure expands, and the entire surface of the steel sheet is finally covered with the secondary recrystallization grains.
  • the temperature of the boundary region is kept relatively constant.
  • a coil-shaped grain-oriented electrical steel sheet is usually disposed in a columnar shape inside a furnace. Therefore, the temperature gradient is preferably applied in the width direction of the steel sheet.
  • the temperature gradient is formed in one direction in the entire width direction of the steel sheet (so that one end serves as the high-temperature end, and the other end serves as the low-temperature end).
  • the nitrogen amount in the steel sheet is 210 ppm or more at the start of secondary recrystallization. Therefore, the amount of the inhibitor increases and the inhibitor becomes thermally stable, so that a sufficient magnetic flux density improving effect can be obtained even under a relatively small temperature gradient.
  • the lower limit of the temperature gradient at which a sufficient magnetic flux density improving effect can be obtained can be reduced.
  • the temperature gradient is 0.5 °C/cm or more.
  • the minimum temperature gradient throughout the coil or the steel sheet is 0.5 °C/cm or more. It is not necessary to limit the upper limit of the temperature gradient. However, even if the temperature gradient exceeds 10.0 °C/cm, the effect is saturated and the equipment load increases. Therefore, the temperature gradient throughout the coil may be 10.0 °C/cm or less.
  • the temperature gradient throughout the coil may be 5.0 °C/cm or less, or may be 2.0 °C/cm or less. Particularly when a relatively uniform temperature gradient is applied, the temperature gradient may be 1.5 °C/cm or less, or may be 1.0 °C/cm or less.
  • the minimum temperature gradient throughout the coil or the steel sheet may be 5.0 °C/cm or less, or may be 2.0 °C/cm or less, and further may be 1.5 °C/cm or less, or may be 1.0 °C/cm or less.
  • the temperature at the position of the boundary region is not constant, depending on the type of the steel sheet and the annealing conditions, the temperature in the boundary region can be known when a preliminary experiment or the like is performed and the temperature at which secondary recrystallization occurs is confirmed under the assumed type of the steel sheet and annealing conditions. Therefore, by applying a temperature gradient in a position where the temperature is around the temperature of the boundary region examined in this way, a temperature gradient can be applied in the boundary region between the primary recrystallization region and the secondary recrystallization region.
  • the temperature of the boundary region is about 900 to 1100°C.
  • a temperature gradient may be applied to a wider range or the entire coil (steel sheet).
  • the effect can be obtained by applying a temperature gradient to the boundary region at least in one period from the generation to the growth of secondary recrystallization grains.
  • the temperature gradient is preferably applied to the boundary region after secondary recrystallization starts and until the entire surface of the steel sheet is covered with secondary recrystallization grains (until the completion of the secondary recrystallization). That is, the temperature gradient may be generated from the beginning to the end of the temperature raising process of the final annealing (until reaching the soaking temperature).
  • the temperature gradient can be applied by increasing the temperature such that the furnace has a temperature difference therein, or by heating and/or cooling the coil ends to increase the temperature such that the coil has a temperature difference therein in the final annealing furnace.
  • the magnitude of the temperature gradient for example, when the temperature gradient is applied in the width direction of the coil, sensors such as thermocouples are arranged at constant intervals (interval at which temperature gradient can be measured, for example, 100 mm interval) in the width direction to measure the temperature history, so that the temperature gradient of each portion in the steel sheet is calculated.
  • the minimum value of the temperature gradient throughout (in the entire region of) the coil can be determined by calculating the temperature gradient of each portion.
  • the temperature gradient varies depending on the size of the furnace, the temperature difference in the furnace, the size and weight of the coil, and the like.
  • physical property values such as thermal diffusivity are calculated by using the results of the temperature history at a plurality of portions of the coil actually measured as described above, and then, for example, the furnace wall temperature is provided as a boundary condition, and the temperature gradient of each portion of the coil is calculated by simulation using a known heat transfer calculation software, Fluent (registered trademark), developed by ANSYS, or the like.
  • Fluent registered trademark
  • various conditions are set so that the temperature gradient of each portion of the coil (for example, a range of arbitrary 100 mm intervals in the width direction of the coil) is calculated in consideration of the variation of the temperature gradient.
  • sensors such as thermocouples are arranged at constant intervals in the width direction (interval at which a difference in the temperature gradient can be measured, for example, 100 mm interval) at a plurality of locations in the radial direction of the coil, and the temperature history in the width direction of each location is measured, whereby the difference in temperature gradient in the radial direction can be calculated.
  • the minimum value of the temperature gradient throughout the coil can be determined from the temperature gradient calculated at each measurement point in the radial direction of the coil.
  • the temperature history in the radial direction of the coil may be measured at three points or more in total, such that each of the steel sheet located on the outermost side of the coil, the steel sheet located in the radial intermediate portion of the coil, and the steel sheet located on the innermost side of the coil has one or more measurement points in the longitudinal direction of the coil.
  • simulation makes it possible to calculate the temperature gradient in the width direction at a plurality of locations in the coil radial direction (for example, each position at intervals of 100 mm in width in the coil radial direction, or each position of the outermost side, the intermediate portion, and the innermost side in the coil radial direction).
  • the temperature gradient When the temperature gradient varies in the coil, the temperature gradient tends to be relatively small on the side of the low-temperature end of the coil, and tends to be relatively small at the position on the radially innermost side of the coil. Therefore, the temperature gradient calculated by measurement or simulation at the position that is on the side of the low-temperature end and the radially innermost side of the coil may be determined as the minimum temperature gradient throughout the coil.
  • the final annealing temperature is preferably 1150 to 1250°C.
  • the annealing time is preferably 10 to 30 hours after the low-temperature side of the temperature gradient of the coil reaches the soaking temperature.
  • the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment may further include an insulating coating-forming step of forming an insulating coating on the surface of the steel sheet.
  • the insulating coating to be formed is not limited, and may be a known coating.
  • the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment may further include a magnetic domain refinement step of performing magnetic domain refinement on the steel sheet.
  • the method of the magnetic domain refinement treatment is not limited. There is a method for narrowing the width of a 180° magnetic domain (performing refinement of a 180° magnetic domain) by forming linear or dotted groove parts extending in a direction intersecting a rolling direction at predetermined intervals in the rolling direction, and a method for narrowing the width of a 180° magnetic domain (performing refinement of a 180° magnetic domain) by forming linear or dotted stress-strain parts or groove parts extending in a direction intersecting a rolling direction at predetermined intervals in the rolling direction.
  • a stress-strain part In a case where a stress-strain part is formed, laser beam irradiation, electron beam irradiation, and the like can be applied.
  • a groove part In a case where a groove part is formed, a mechanical groove-forming method using a gear or the like, a chemical groove-forming method by electrolytic etching, a thermal groove-forming method by laser irradiation, and the like can be applied.
  • the insulating coating may be formed again to repair the damage.
  • the silicon steel material is heated to 1280 to 1400°C and held for 1 hour, and then hot-rolled to prepare a hot rolled sheet having a sheet thickness of 2.3 mm.
  • Each of the hot rolled sheets except for No. 7 is heated to 1000°C and subjected to annealing (hot-rolled sheet annealing) for 60 seconds.
  • the hot rolled sheet is cold-rolled to a thickness of 0.22 mm to obtain a steel sheet (cold rolled sheet).
  • a sample steel sheet having a length of 200 mm in the rolling direction and a length of 600 mm in the width direction is cut out from the steel sheet.
  • the sample steel sheet is subjected to decarburization annealing in which the sample steel sheet is held at 750 to 900°C for 100 seconds, and the primary recrystallization grain size is controlled to be 5 to 20 ⁇ m.
  • the primary recrystallization grain size is measured after the decarburization annealing step and before the final annealing.
  • nitriding treatment is performed at least in one timing of: during the temperature raising process and soaking process in the decarburization annealing step; between the decarburization annealing step and the final annealing step; and during the temperature raising process in the final annealing step and before the start of the secondary recrystallization, and the nitrogen amount after the final nitriding treatment step is controlled to be 160 to 380 ppm.
  • Between decarburization annealing step and final annealing step means that nitriding treatment is performed one time "between the completion of the decarburization annealing step and the start of the final annealing step", and “Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization” means that nitriding treatment is performed two times, "between the completion of the decarburization annealing step and the start of the final annealing step” and "from the start of the final annealing step to the start of the secondary recrystallization in the temperature raising process in the final annealing step".
  • the steel sheet is applied with an annealing separator containing MgO as a main component, and then subjected to final annealing such that the steel sheet end has a high temperature, and a temperature gradient of 0 to 5.0 °C/cm is applied to the entire region in the direction perpendicular to the rolling direction (width direction) to generate secondary recrystallization.
  • the average temperature rising rate from the start of the secondary recrystallization to the completion of the secondary recrystallization in the boundary region is 10 °C/hr
  • the final annealing temperature is 1200°C
  • the soaking time is 30 hours.
  • the temperature gradient is uniformly applied throughout the sample steel sheet.
  • the temperature gradient is applied by increasing the temperature such that the furnace has a temperature difference therein.
  • the magnitude of the temperature gradient is controlled by raising the temperature while measuring the temperature at intervals of 100 mm in the width direction of the steel sheet.
  • a sample of 60 mm in the width direction and 200 mm in the rolling direction is collected from the obtained steel sheet, and magnetic properties this sample is measured by the SST method (see JISC2556:2015 Annex JA) to measure the magnetic flux density B8 in the rolling direction.
  • Tables 1-1 to 1-3 show the results.
  • Hot rolling step Hot-rolled sheet annealing step Decarburization annealing step Nitriding treatment step Final annealing step Magnetic flux density B8 (T) Note Temperature raising process Heating temperature (°C) Annealing temperature (°C) Holding time (sec) Annealing temperature (°C) Holding time (sec) Primary recrystallization grain size ( ⁇ m) Performing timing Nitrogen amount after nitriding treatment (ppm) Temperature gradient (°C/cm) 17 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step 210 1.5 1.957 Inventive Example 18 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 0.0 1.920 Comparative Example 19 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 0.5 1.945 Inventive Example 20 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210
  • Hot rolling step Hot-rolled sheet annealing step Decarburization annealing step Nitriding treatment step Final annealing step Magnetic flux density B8 (T) Note Temperature raising process Heating temperature (°C) Annealing temperature (°C) Holding time (sec) Annealing temperature (°C) Holding time (sec) Primary recrystallization grain size ( ⁇ m) Performing timing Nitrogen amount after nitriding treatment (ppm) Temperature gradient (°C/cm) 38 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 0.5 1.925 Comparative Example 39 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 1.0 1.932 Comparative Example 40 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 1.5 1.938 Comparative Example 41 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 300 0.0 1.920 Comparative
  • a silicon steel material (slab) having a chemical composition shown in Table 2 (unit: mass%, balance: Fe and impurities) is obtained by casting.
  • the silicon steel material is heated to 1350°C and held for 1 hour, and then hot-rolled to prepare a hot rolled sheet having a sheet thickness of 2.3 mm.
  • the hot rolled sheet is held at an annealing temperature of 950 to 1100°C for 30 to 120 seconds for hot-rolled sheet annealing.
  • the hot rolled sheet after the hot rolled sheet annealing is cold-rolled to a thickness of 0.22 mm to obtain a steel sheet (cold rolled sheet).
  • a sample steel sheet having a length of 200 mm in the rolling direction and a length of 600 mm in the width direction is cut out from the steel sheet.
  • the sample steel sheet is subjected to decarburization annealing, and the primary recrystallization grain size is controlled to be 10 ⁇ m.
  • the annealing temperature is 750 to 800°C, and the holding time is 50 to 200 seconds.
  • Nitriding treatment is performed between the decarburization annealing step and the final annealing step, and the nitrogen amount is controlled to be 210 ppm. The nitriding treatment is performed one time between the completion of the decarburization annealing step and the start of the final annealing step.
  • the steel sheet is applied with an annealing separator containing MgO as a main component, and then subjected to final annealing such that the steel sheet end has a high temperature, and a temperature gradient of 0.5 °C/cm is applied to the entire region in the direction perpendicular to the rolling direction (width direction) to generate secondary recrystallization.
  • the final annealing temperature is 1150 to 1250°C, and the soaking time is 10 to 30 hours.
  • the temperature gradient is uniformly applied throughout the sample steel sheet.
  • the temperature gradient is applied by increasing the temperature such that the furnace has a temperature difference therein.
  • the magnitude of the temperature gradient is controlled by raising the temperature while measuring the temperature at intervals of 100 mm in the width direction of the steel sheet.
  • a sample of 60 mm in the width direction and 200 mm in the rolling direction is collected from the obtained steel sheet, and magnetic properties of this sample is measured by the SST method (see JISC2556:2015 Annex JA) to measure the magnetic flux density B8 in the rolling direction.
  • the present invention it is possible to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method of manufacturing a grain-oriented electrical steel sheet capable of obtaining a sufficient magnetic flux density improving effect even under a small temperature gradient. Therefore, the present invention has high industrial applicability.

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Abstract

The method of manufacturing a grain-oriented electrical steel sheet includes: a hot rolling step; a hot-rolled sheet annealing step; a cold rolling step; a decarburization annealing step; an annealing separator applying step; a nitriding treatment step; and a final annealing step, wherein the final annealing step has a temperature raising process and a soaking process, and a temperature gradient of 0.5 °C/cm or more is generated in a boundary region between a primary recrystallization region and a secondary recrystallization region at least in one period from the start of secondary recrystallization to completion of the secondary recrystallization in the temperature raising process; and the nitriding treatment step is performed by annealing in an atmosphere containing a gas having nitriding ability at least in one stage of: during the decarburization annealing step; between the decarburization annealing step and the final annealing step; and during the temperature raising process in the final annealing step and before the start of the secondary recrystallization, so that the nitrogen amount in the steel sheet is 210 ppm or more based on mass after the nitriding treatment step.

Description

    TECHNICAL FIELD
  • The present invention relates to a method of manufacturing a grain-oriented electrical steel sheet.
  • Priority is claimed on Japanese Patent Application No. 2023-005565, filed January 18, 2023 , the content of which is incorporated herein by reference.
    • BACKGROUND ART
  • The grain-oriented electrical steel sheet (also referred to as grain-oriented silicon steel sheet) is a soft magnetic material, and is mainly used as an iron core material of a transformer. Therefore, the grain-oriented electrical steel sheet is required to have a small energy loss (low iron loss). For example, the magnetic flux density: B8 (magnetic flux density in a magnetic field of 800 A/m) is the most dominant factor of iron loss characteristics. It is known that the higher the value of the magnetic flux density: B8, the lower the iron loss, and the better the iron loss characteristics. In addition, the iron core can be downsized as the value of the magnetic flux density: B8 becomes higher, which is advantageous in terms of the device configuration of the transformer and also advantageous in terms of the manufacturing cost of the transformer. In order to increase the value of the magnetic flux density: B8, it is important to highly align the crystal orientation. The crystal orientation control is achieved using a catastrophic grain growth phenomenon called secondary recrystallization.
  • Hitherto, many inventions relating to a grain-oriented electrical steel sheet having a high magnetic flux density have been proposed. However, in industrially produced grain-oriented silicon steel sheets investigated so far, the magnetic flux density (B8) thereof is smaller than the theoretical upper limit of silicon steel, and there is still room for significant improvement.
  • In order to improve the magnetic flux density, for example, Patent Document 1 discloses a method of manufacturing a grain-oriented electrical steel sheet having a high magnetic flux density in which a silicon steel slab containing 0.015% or less of C, 4% or less of Si, 0.012% or less of S, 0.020 to 0.065% of acid-soluble Al, and 0.0030 to 0.0095% of T.N is heated at 1270°C or lower and then hot-worked into a hot rolled sheet, the hot rolled sheet is coiled at 700 to 950°C and then cold-rolled at a rolling reduction of 65% or more, the steel sheet is annealed for primary recrystallization for a short time, and then the steel sheet is subjected to final annealing at high temperature including treatment of growing secondary recrystallization grains while applying a temperature gradient of 2 °C/cm or more to the steel sheet in the boundary portion between the primary recrystallization region and the secondary recrystallization region.
  • In addition, Patent Document 2 discloses a method of manufacturing a grain-oriented silicon steel sheet having an ultra-low iron loss including achieving crystal orientation control through secondary recrystallization and a smooth steel sheet surface to manufacture a grain-oriented electrical steel sheet having an ultra-low iron loss at low cost also for a material having a thin sheet thickness (for example, 0.13 mm), which has been difficult to manufacture conventionally. Patent Document 2 discloses that it is necessary to raise the temperature to 1000 to 1100°C at a temperature rising rate of 50 °C/hr or more in the final annealing in order to secure a temperature gradient of at least 2 °C/cm.
  • Further, for example, Patent Document 3 discloses a method of manufacturing a grain-oriented silicon steel sheet (band) having a high magnetic flux density in which secondary recrystallization proceeds while the steel sheet (band) is applied with a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region during the manufacturing process of a grain-oriented silicon steel sheet (band).
  • In addition, for example, Patent Documents 4 and 5 disclose equipment and methods for imparting a temperature gradient to a coiled steel sheet.
    • Citation List Patent Document
    • Patent Document 1: Japanese Examined Patent Application Publication No. S59-41488
    • Patent Document 2: Japanese Unexamined Patent Application, First Publication No. H05-311238
    • Patent Document 3: Japanese Examined Patent Application Publication No. S58-50295
    • Patent Document 4: Japanese Unexamined Patent Application, First Publication No. S57-164935
    • Patent Document 5: Japanese Unexamined Patent Application, First Publication No. S58-1019
    SUMMARY OF INVENTION Technical Problem
  • As described above, in the techniques described in Patent Documents 1 and 2, it is necessary that a temperature gradient of 2 °C/cm or more be applied during final annealing. It is thought that the equipment and methods disclosed in Patent Documents 4 and 5 or the like are adopted to apply a temperature gradient. However, using the equipment and methods disclosed therein, it is difficult to control the temperature gradient to be constant throughout an industrial scale coil in the longitudinal direction and in the width direction, and to control the temperature gradient to be high throughout the same, and there are regions with a low-temperature gradient of about 0.5 °C/cm (small temperature gradient) in some parts. In such a low-temperature gradient region, it is difficult to sufficiently improve the magnetic flux density.
  • The present inventors calculated the temperature gradient of each portion of a coil by simulation using a known heat transfer calculation software, Fluent (registered trademark), developed by ANSYS, and found that even when a temperature gradient of 2 °C/cm or more is applied, a region having a low-temperature gradient of about 0.5 °C/cm (small temperature gradient) exists in some parts of the coil. It was found that when a coil is applied with a temperature gradient, particularly to a large temperature gradient, the temperature gradient tends to be smaller inside the coil than outside the coil. That is, for example, even when the temperature gradient is 2 °C/cm or more outside the coil, there is a low-temperature gradient of less than 2 °C/cm in some regions inside the coil or the like. In addition, when a temperature gradient is applied in the width direction of a coil, the temperature gradient tends to be smaller on the low-temperature end than on the high-temperature end. For example, even when the temperature gradient is 2 °C/cm or more on the high-temperature end of the coil, there may be a low-temperature gradient of less than 2 °C/cm in some parts on the low-temperature end or the like. Therefore, it is difficult to apply a temperature gradient of 2 °C/cm or more throughout a coil.
  • For this reason, in order to obtain a sufficient effect of improving the magnetic flux density throughout a coil, a method for obtaining the effect of improving the magnetic flux density even under a smaller temperature gradient has been desired.
  • Patent Document 3 discloses that an effect of improving B8 characteristics is recognized by imparting a temperature gradient of 0.5 °C/cm. However, Patent Document 3 indicates that a remarkable effect is obtained at 2 °C/cm or more. In fact, the B8 value of a grain-oriented electrical steel sheet having a Si content of 2.95% is about 1.92 T under a temperature gradient of 0.5 °C/cm, which means that a certain effect of improving the magnetic flux density is obtained, but it cannot be said to be sufficient for the recent advanced requirements.
  • The present invention has been made in view of the above problem. An object of the present invention is to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method for manufacturing a grain-oriented electrical steel sheet stably having a high magnetic flux density throughout a coil by obtaining a sufficient effect of improving magnetic flux density even under a small temperature gradient.
    • Solution to Problem
  • On the premise of a method of performing final annealing while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region, the present inventors examined a method for obtaining a sufficient effect of improving the magnetic flux density even under a relatively small temperature gradient (even when the lower limit of the temperature gradient is small in a case where a large temperature gradient part and a small temperature gradient part are generated).
  • As a result, it was found that, when the primary recrystallization grain size is 15 µm or less and a nitriding treatment step is performed so that the steel sheet has a nitrogen amount of 210 ppm or more before secondary recrystallization, a sufficient effect of improving the magnetic flux density is obtained even under a relatively small temperature gradient.
  • The present invention has been made in view of the above findings. The gist of the present invention is as follows.
    1. [1] In an embodiment of the present invention, a method of manufacturing a grain-oriented electrical steel sheet includes: a hot rolling step of heating a silicon steel material containing, in terms of mass%, 0.80 to 7.00% of Si to a temperature of higher than 1300°C and hot rolling the silicon steel material, to obtain a hot rolled sheet; a hot-rolled sheet annealing step of annealing the hot rolled sheet; a cold rolling step of cold-rolling the hot rolled sheet after the hot rolling step or after the hot-rolled sheet annealing step to obtain a steel sheet having a final sheet thickness; a decarburization annealing step of decarburization-annealing the steel sheet after the cold rolling step to obtain a steel sheet having a primary recrystallization grain size of 15 µm or less; an annealing separator applying step of applying an annealing separator on the steel sheet after the decarburization annealing step and coiling the steel sheet into a coil shape; a nitriding treatment step of increasing a nitrogen amount in the steel sheet; and a final annealing step of final-annealing the steel sheet coiled into a coil shape, wherein the final annealing step has a temperature raising process and a soaking process, and a temperature gradient of 0.5 °C/cm or more is generated in a boundary region between a primary recrystallization region and a secondary recrystallization region at least in one period from the start of secondary recrystallization to completion of the secondary recrystallization in the temperature raising process; and the nitriding treatment step is performed by annealing in an atmosphere containing a gas having nitriding ability at least in one stage of: during the decarburization annealing step; between the decarburization annealing step and the final annealing step; and during the temperature raising process in the final annealing step and before the start of the secondary recrystallization, so that the nitrogen amount in the steel sheet is 210 ppm or more based on mass after the nitriding treatment step.
    2. [2] In the method of manufacturing a grain-oriented electrical steel sheet according to [1], the silicon steel material may include, as a chemical composition, in terms of mass%, 0.80 to 7.00% of Si, 0.15% or less of C, 0.010 to 0.065% of acid-soluble Al, 0.004 to 0.012% of N, 0.01 to 0.50% of Mn, 0.01 to 0.05% in total of S and Se, 0 to 0.30% of Cr, 0 to 0.4% of Cu, 0 to 0.5% of P, 0 to 1.00% of Ni, and a balance of Fe and impurities.
    Advantageous Effects of Invention
  • According to the embodiment of the present invention, it is possible to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method of manufacturing a grain-oriented electrical steel sheet capable of obtaining a sufficient effect of improving magnetic flux density even under a small temperature gradient.
    • DESCRIPTION OF EMBODIMENTS
  • Hereinafter, a method of manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention (a method of manufacturing a grain-oriented electrical steel sheet according to the embodiment) will be described.
  • The method of manufacturing a grain-oriented electrical steel sheet according to the embodiment includes:
    1. (i) a hot rolling step of heating a silicon steel material having a predetermined chemical composition to a temperature of higher than 1300°C and hot rolling the silicon steel material, to obtain a hot rolled sheet;
    2. (ii) a hot-rolled sheet annealing step of annealing the hot rolled sheet;
    3. (iii) a cold rolling step of cold-rolling the hot rolled sheet after the hot rolling step or after the hot-rolled sheet annealing step to obtain a steel sheet having a final sheet thickness;
    4. (iv) a decarburization annealing step of decarburization-annealing the steel sheet after the cold rolling step to obtain a steel sheet having a primary recrystallization grain size of 15 µm or less;
    5. (v) an annealing separator applying step of applying an annealing separator on the steel sheet after the decarburization annealing step and coiling the steel sheet into a coil shape;
    6. (vi) a nitriding treatment step of increasing a nitrogen amount in the steel sheet; and
    7. (vii) a final annealing step of final-annealing the steel sheet coiled into a coil shape.
  • Hereinafter, the conditions of each step will be described.
    • [Hot Rolling Step]
  • In the hot rolling step, a silicon steel material such as a slab having a chemical composition described later is heated to a temperature of higher than 1300°C and hot rolling, to obtain a hot rolled sheet.
  • When the heating temperature is higher than 1300°C, the precipitate acting as an inhibitor completely becomes a solid solution, and is finely precipitated during the hot rolling and the subsequent annealing steps, so that grain growth is suppressed from the decarburization annealing step to the final annealing step. The heating temperature may be 1310°C or higher, or may be 1350°C or higher.
  • The upper limit of the heating temperature is not limited. However, when the heating temperature is excessively increased, good magnetic characteristics may fail to be obtained due to insufficient secondary recrystallization. Therefore, the heating temperature is preferably 1450°C or lower.
  • The hot rolling conditions other than the heating temperature are not limited, and may be in a known range according to required characteristics and the like.
  • In addition, the silicon steel material to be subjected to hot rolling is obtained by smelting steel in a converter, an electric furnace, or the like, subjecting the molten steel to a vacuum degassing treatment as necessary, and then subjecting the molten steel to continuous casting or blooming after an ingot is made.
  • The silicon steel material contains 0.80 to 7.00% of Si in terms of mass%. Preferably, the silicon steel material includes, as the chemical composition, in terms of mass%, 0.80 to 7.00% of Si, 0.15% or less of C, 0.010 to 0.065% of acid-soluble Al, 0.004 to 0.012% of N, 0.01 to 0.50% of Mn, 0.01 to 0.05% in total of S and Se, 0 to 0.30% of Cr, 0 to 0.4% of Cu, 0 to 0.5% of P, 0 to 1.00% of Ni, and a balance of Fe and impurities.
  • The reason for the content of each element will be described. Hereinafter, % regarding the content is mass%.
    • (Si: 0.80 to 7.00%)
  • When the Si content is less than 0.80%, γ transformation occurs during the final annealing, and the crystal orientation of the steel sheet is impaired. In addition, when Si is contained, electrical resistance is increased and iron loss characteristics are improved. Therefore, in the silicon steel material, the Si content is 0.80% or more. The Si content is preferably 1.50% or more, more preferably 2.00% or more, and still more preferably 2.50% or more.
  • On the other hand, when the Si content is more than 7.00%, it is extremely difficult to perform cold rolling, and there is a possibility of cracking during rolling. Therefore, the Si content is 7.00% or less. As a range suitable for industrial production, the Si content may be 4.80% or less, or may be 4.00% or less.
    • (C: 0.15% or less)
  • C is an effective element for controlling the primary recrystallization structure, but has an adverse effect on the magnetic characteristics. Therefore, it is necessary to perform decarburization before the final annealing. When the C content is more than 0.15% in the silicon steel material, the decarburization annealing time becomes long, and industrial productivity is impaired. Therefore, the C content is preferably 0.15% or less. The C content is more preferably 0.12% or less. The lower limit of the C content is not particularly limited, but is preferably 0.02% or more, more preferably 0.03% or more, and further preferably 0.05% or more in consideration of industrial productivity and magnetic properties of products.
    • (Acid-soluble Al: 0.010 to 0.065%)
  • Acid-soluble Al (sol.Al) is an element that binds to N and functions as an inhibitor as AIN or (Al, Si)N. As a range in which the secondary recrystallization is stabilized, the acid-soluble Al content is preferably 0.010 to 0.065%. The acid-soluble Al content may be 0.040% or less, and further, may be 0.030% or less.
    • (N: 0.004 to 0.012%)
  • N is an element that binds to Al and functions as an inhibitor. When the N content is less than 0.004%, a sufficient amount of inhibitor cannot be obtained. Therefore, the N content is preferably 0.004% or more. The N content is more preferably 0.006% or more, still more preferably 0.007% or more.
  • On the other hand, when the N content is more than 0.012%, pores called blisters may be generated in the steel sheet during cold rolling. Therefore, the N content is preferably 0.012% or less.
  • The silicon steel material may contain, as the chemical composition, the above elements, and the balance may be Fe and impurities. On the other hand, in order to improve various properties, the following elements may be further contained.
  • The following elements are also allowed to be contained as impurities as long as they fall within the range described later.
    • (Mn: 0.01 to 0.50%)
  • Mn is an element that functions as an inhibitor as MnS or MnSe. When the Mn content is less than 0.01%, a sufficient amount of inhibitor cannot be obtained. Therefore, the Mn content is preferably 0.01% or more. The Mn content is more preferably 0.03% or more, and still more preferably 0.06% or more.
  • On the other hand, when the Mn content is more than 0.50%, it is difficult to make a solid solution of Mn during heating of the silicon steel material, which is not preferable. In addition, when the Mn content is more than 0.50%, the precipitation size of MnS and MnSe as an inhibitor tends to be coarsened, and the optimum size distribution as an inhibitor is impaired, which is not preferable. Therefore, the Mn content is preferably 0.50% or less. The Mn content is more preferably 0.30% or less, and still more preferably 0.28% or less.
  • Mn is an element having an effect of increasing specific resistance and reducing iron loss. Mn is an effective element for preventing the occurrence of cracking in hot rolling caused by S or Se. In order to prevent the occurrence of cracking, the Mn content is preferably in a range satisfying Mn/(S + Se) ≥ 4 in relation to the total amount of S and Se.
    • (S and Se: 0.01 to 0.05% in total)
  • S and Se form an inhibitor together with Mn. When the total content of S and Se is less than 0.01%, a sufficient amount of inhibitor cannot be obtained. Therefore, the total content of S and Se is preferably 0.01% or more. The total content of S and Se is more preferably 0.02% or more.
  • On the other hand, when the total content of S and Se exceeds 0.05%, hot embrittlement is caused, and hot rolling is significantly difficult. Therefore, the total content of S and Se is preferably 0.05% or less. The total content of S and Se is preferably 0.04% or less.
    • (Cr: 0 to 0.30%)
  • Cr is an element that brings the composition and amount of the oxide layer of the decarburization annealing into a preferable state and promotes the formation of a glass coating. Thus, Cr may be included.
  • On the other hand, when the Cr content is more than 0.30%, decarburization is inhibited. Therefore, the Cr content is preferably 0.30% or less.
    • (Cu: 0 to 0.4%)
  • Cu is an effective element for increasing specific resistance and reducing iron loss. Thus, Cu may be included.
  • On the other hand, when the Cu content is more than 0.4%, the iron loss reduction effect is saturated, and a surface defect called "copper scab" is caused during hot rolling. Therefore, the Cu content is preferably 0.4% or less.
    • (P: 0 to 0.5%)
  • P is an effective element for increasing specific resistance and reducing iron loss. Thus, P may be included.
  • On the other hand, when the P content is more than 0.5%, the rollability is deteriorated. Therefore, the P content is preferably 0.5% or less.
    • (Ni: 0 to 1.00%)
  • Ni is an effective element for increasing specific resistance and reducing iron loss. In addition, Ni is an effective element for controlling the metallographic structure of the hot rolled sheet to improve magnetic characteristics. Thus, Ni may be included.
  • On the other hand, when the Ni content exceeds 1.00%, secondary recrystallization becomes unstable. Therefore, the Ni content is preferably 1.00% or less.
  • In addition to the above-described elements, for example, B, O, Mg, Ca, Ti, Mo, V, Nb, Sn, Sb, and Bi may be each contained as impurities in an amount of 0.10% or less. Impurity refers to an element that is mixed from a raw material or in a manufacturing process and does not clearly affect the characteristics of the grain-oriented electrical steel sheet obtained by the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment.
  • The chemical composition of the silicon steel material may be measured by a known method.
  • For example, the chemical composition may be measured using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Note that Al may be measured by ICP-AES using, as acid-soluble Al, a filtrate after a sample is thermally decomposed with an acid. Si may be measured by the silicon dioxide weight method, C and S may be measured by the combustion-infrared absorption method, and N may be measured by the inert gas fusion-thermal conductivity method. O may be measured using the inert gas fusion-non-dispersive infrared absorption method.
  • The above chemical composition refers to the components of the silicon steel sheet as a base metal. When the grain-oriented electrical steel sheet as a measurement sample has a glass coating, an insulating coating, or the like on the surface, the chemical composition is measured after these coatings are removed by a known method.
    • [Hot-Rolled sheet Annealing Step]
  • After the hot rolling step, the hot rolled sheet obtained by hot rolling is subjected to annealing (hot rolled sheet annealing) in order to enhance magnetic characteristics. When the hot-rolled sheet annealing is not performed, sufficient magnetic characteristics cannot be obtained. The annealing condition may be, for example, a condition of holding at 900 to 1200°C for 30 seconds to 30 minutes. The annealing temperature may be 950 to 1050°C.
    • [Cold Rolling Step]
  • In the cold rolling step, the hot rolled sheet after the hot rolling step or after the hot-rolled sheet annealing step is subjected to cold rolling to obtain a steel sheet (cold rolled sheet) having a sheet thickness equal to the final sheet thickness (the sheet thickness of the completed grain-oriented electrical steel sheet (when a glass coating or an insulating coating is formed on the surface thereof, the sheet thickness of the base steel sheet excluding the coatings)). The cold rolling may be performed one time (in series without intervening intermediate annealing) or two or more times with intervening annealing (intermediate annealing).
  • For the cold rolling, in order to develop a preferable primary recrystallization orientation, the final rolling reduction is preferably 80% or more. The final rolling reduction is a cumulative rolling reduction of cold rolling, and when intermediate annealing is performed, the final rolling reduction is a cumulative rolling reduction of cold rolling after the final intermediate annealing.
    • [Decarburization Annealing Step]
  • In the decarburization annealing step, the steel sheet after the cold rolling step is subjected to decarburization annealing.
  • In the decarburization annealing, the steel sheet is primarily-recrystallized and C, which adversely affects magnetic characteristics, is removed from the steel sheet. In the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment, the primary recrystallization grain size (the grain size of the primary recrystallization grain) is 15 µm or less. The primary recrystallization grain size may be 13 µm or less, and further may be 10 µm or less.
  • In order to manufacture a steel sheet having a high magnetic flux density by providing a temperature gradient, it is necessary to preferentially grow only { 110} <001> oriented grains having good magnetic characteristics from the high-temperature side to the low-temperature side along the temperature gradient. For this purpose, it is necessary to appropriately control the grain growth by the primary recrystallization grain size and the inhibitor. When the primary recrystallization grain size (the grain size of the primary recrystallization grain) is reduced, the driving force for grain growth during secondary recrystallization is enhanced. In addition, when the steel sheet is nitridized through the nitriding treatment described later, the inhibitor can be thermally stabilized. When the primary recrystallization grain size is 15 µm or less to enhance the driving force and the steel sheet has a nitrogen amount of 210 ppm (0.0210 mass%) or more based on mass through the nitriding treatment to thermally stabilize the inhibitor, it is possible to preferentially grow only {110} <001> oriented grains having good magnetic characteristics even under a low-temperature gradient.
  • In order to reduce the primary recrystallization grain size, first, the heating temperature of the silicon steel material in the hot rolling step described above is higher than 1300°C, and then the annealing temperature and time may be controlled in the decarburization annealing step. The annealing temperature in the decarburization annealing step is not limited, and may be, for example, 700°C or higher and 850°C or lower, and may be 750°C or higher, or 800°C or lower. In addition, the holding time of the annealing temperature is not limited, and may be 10 to 600 seconds.
  • The primary recrystallization grain size after the decarburization annealing step is measured by the following method.
  • A sample is collected from the steel sheet after the decarburization annealing step and before the final annealing step, a cross section of the sample parallel to the rolling direction and parallel to the sheet thickness direction is observed with an optical microscope, the average grain size (circle equivalent diameter) of the primary recrystallization grains in the entire thickness of the cross section is determined by image analysis, and the average value is determined as the primary recrystallization grain size. At this time, in order to reduce variation, one visual field or more visual fields are observed, and 500 or more grains are observed. When two or more visual fields are observed, it is preferable to observe two or more positions separated by 50 mm or more in a linear distance in order to reduce the influence of variation in the primary recrystallization grain size due to the position in the steel sheet.
    • [Annealing Separator Applying Step]
  • In the annealing separator applying step, the steel sheet after the decarburization annealing step is applied with an annealing separator, and then coiled into a coil shape.
  • The annealing separator to be applied may be a known one, but an annealing separator containing magnesia as a main component is preferable. By applying an annealing separator containing magnesia as a main component and performing the subsequent final annealing, a glass coating (forsterite coating) is formed on the surface of the steel sheet.
    • [Nitriding Treatment Step]
  • In the nitriding treatment step, the nitrogen amount in the steel sheet is increased. The nitriding treatment step is performed at least in one stage of: during the decarburization annealing step; between the decarburization annealing step and the final annealing step; and after the start of the final annealing step and before the start of the secondary recrystallization in the temperature raising process in the final annealing step. Between the decarburization annealing step and the final annealing step means between the completion of the decarburization annealing step and the start of the final annealing step. The nitriding treatment step is preferably performed after the completion of the decarburization annealing step and before the start of the annealing separator applying step.
  • However, regardless of which stage the nitriding treatment step is performed in, the nitrogen amount in the steel sheet is required to be 210 ppm (0.0210 mass%) or more based on mass after the final nitriding treatment step. When the nitrogen amount in the steel sheet before the start of secondary recrystallization is increased, the amount of the inhibitor is increased, and the inhibitor becomes thermally stable. As a result, a sufficient magnetic flux density improving effect can be obtained even under a relatively small temperature gradient. The nitrogen amount may be 250 ppm or more, and further, may be 300 ppm or more. On the other hand, when the nitrogen amount is more than 350 ppm, the effect of improving the magnetic flux density may be saturated, and there is also a possibility that purification after secondary recrystallization will be disadvantageous. Therefore, the nitrogen amount is preferably 350 ppm or less.
  • Conventionally, when final annealing is performed by applying a temperature gradient, the nitrogen amount in the steel sheet is usually 200 ppm or less. For example, JP S59-215419 A discloses that when secondary recrystallization annealing is performed while the boundary region between the primary recrystallization region and the secondary recrystallization region is applied with a temperature gradient in the final annealing, the nitrogen content in the steel sheet is 130 to 200 ppm at the start of secondary recrystallization. JP S59-215419 A describes that the magnetic flux density improving effect is saturated at a nitrogen content of 180 to 200 ppm.
  • Conventionally, when a silicon steel material is heated at a high temperature to utilize MnS and MnSe as an inhibitor, a nitriding treatment step has not been usually performed.
  • On the other hand, even under heating at a high temperature, the present inventors have found that when the primary recrystallization grain size is 15 µm or less and the nitrogen amount is increased to 210 ppm or more, the lower limit of the temperature gradient at which high magnetic flux density (for example, B8 is stably 1.940 T or more) can be achieved is expanded compared with the conventional case (high B8 is stably obtained even when the temperature gradient is about 0.5 °C/cm).
  • Examples of the method for increasing the nitrogen amount in the steel sheet include a method of annealing the steel sheet in an atmosphere containing a gas having nitriding ability to control the nitrogen amount in the steel sheet.
  • In addition to the above, the nitrogen amount in the steel sheet may be increased by adding a powder having nitriding ability such as MnN to an annealing separator in the temperature raising process in the final annealing step.
  • The nitrogen amount in the steel sheet after the nitriding treatment can be measured by a known method using, for example, an oxygen-nitrogen-hydrogen analyzer (EMGA-930) manufactured by HORIBA, Ltd. or an apparatus equivalent thereto. As the known method, a general analysis method such as the inert gas fusion-thermal conductivity method can be used. A sample having an arbitrary size may be collected from the steel sheet after the nitriding treatment step in the manufacturing process, and measured using these devices and methods.
    • [Final Annealing Step]
  • In the final annealing step, the steel sheet coiled into a coil shape is subjected to final annealing.
  • The final annealing step includes: a temperature raising process of heating to a final annealing temperature for secondary recrystallization; and a soaking process of holding the steel sheet at the final annealing temperature.
    • <Temperature Raising Process>
  • In the final annealing step, under the state where the nitrogen amount in the steel sheet is controlled to be 210 ppm or more based on mass in the nitriding treatment step, a temperature gradient of 0.5 °C/cm or more is generated in a boundary region between a primary recrystallization region and a secondary recrystallization region at least in one period from the start of secondary recrystallization to completion of the secondary recrystallization in the temperature raising process, and { 110} <001> oriented grains are preferentially grown through secondary recrystallization. Even if a temperature gradient is applied at a time other than the above time, for example, before the final annealing, a similar effect cannot be obtained.
  • The temperature rising rate is not limited as long as the temperature gradient is satisfied, and may be 50 °C/h or less.
  • In the final annealing, secondary recrystallized grains are generated in a portion heated to the secondary recrystallization temperature or higher. When the steel sheet is heated in a state where a temperature gradient exists in a certain direction, secondary recrystallization proceeds from the region where the temperature is equal to or higher than the secondary recrystallization temperature; and between the above region and the region where the secondary recrystallization temperature has not been reached and the primary recrystallization structure still remains, a region where primary recrystallization grains and secondary recrystallization grains are mixed in the sheet thickness direction (boundary region) is generated along the isotherm. As the steel sheet is heated and the temperature increases, this boundary region moves along the temperature gradient to the region where the primary recrystallization structure remains, so that the region that has become the secondary recrystallization structure expands, and the entire surface of the steel sheet is finally covered with the secondary recrystallization grains. Throughout this process, the temperature of the boundary region is kept relatively constant. Regarding the direction of the temperature gradient, in the final annealing, a coil-shaped grain-oriented electrical steel sheet is usually disposed in a columnar shape inside a furnace. Therefore, the temperature gradient is preferably applied in the width direction of the steel sheet. When a temperature gradient is applied in the width direction, the temperature gradient is formed in one direction in the entire width direction of the steel sheet (so that one end serves as the high-temperature end, and the other end serves as the low-temperature end).
  • As described above, it is not easy to apply a temperature gradient of 2.0 °C/cm or more throughout a coil, and problems of productivity, variations in characteristics in the steel sheet, and the like may arise. However, in the method of manufacturing a grain-oriented electrical steel sheet according to the embodiment, the nitrogen amount in the steel sheet is 210 ppm or more at the start of secondary recrystallization. Therefore, the amount of the inhibitor increases and the inhibitor becomes thermally stable, so that a sufficient magnetic flux density improving effect can be obtained even under a relatively small temperature gradient. When the temperature gradient varies, the lower limit of the temperature gradient at which a sufficient magnetic flux density improving effect can be obtained can be reduced. However, when the temperature gradient is less than 0.5 °C/cm, the effect of improving the magnetic flux density cannot be sufficiently obtained. Therefore, the temperature gradient is 0.5 °C/cm or more. When the temperature gradient varies in each portion of the coil or the steel sheet, the minimum temperature gradient throughout the coil or the steel sheet is 0.5 °C/cm or more. It is not necessary to limit the upper limit of the temperature gradient. However, even if the temperature gradient exceeds 10.0 °C/cm, the effect is saturated and the equipment load increases. Therefore, the temperature gradient throughout the coil may be 10.0 °C/cm or less. In the present application, since a sufficient magnetic flux density improving effect can be obtained even under a relatively small temperature gradient, the temperature gradient throughout the coil may be 5.0 °C/cm or less, or may be 2.0 °C/cm or less. Particularly when a relatively uniform temperature gradient is applied, the temperature gradient may be 1.5 °C/cm or less, or may be 1.0 °C/cm or less. When the temperature gradient varies in each portion of the coil or the steel sheet, the minimum temperature gradient throughout the coil or the steel sheet may be 5.0 °C/cm or less, or may be 2.0 °C/cm or less, and further may be 1.5 °C/cm or less, or may be 1.0 °C/cm or less.
  • Regarding the application of a temperature gradient, although the temperature at the position of the boundary region is not constant, depending on the type of the steel sheet and the annealing conditions, the temperature in the boundary region can be known when a preliminary experiment or the like is performed and the temperature at which secondary recrystallization occurs is confirmed under the assumed type of the steel sheet and annealing conditions. Therefore, by applying a temperature gradient in a position where the temperature is around the temperature of the boundary region examined in this way, a temperature gradient can be applied in the boundary region between the primary recrystallization region and the secondary recrystallization region. For example, when the steel sheet contains MnS and AlN as an inhibitor and has a Si content of about 3 mass%, the temperature of the boundary region is about 900 to 1100°C.
  • When the boundary region is not clear, a temperature gradient may be applied to a wider range or the entire coil (steel sheet).
  • In addition, the effect can be obtained by applying a temperature gradient to the boundary region at least in one period from the generation to the growth of secondary recrystallization grains. However, in order to obtain a sufficient effect, the temperature gradient is preferably applied to the boundary region after secondary recrystallization starts and until the entire surface of the steel sheet is covered with secondary recrystallization grains (until the completion of the secondary recrystallization). That is, the temperature gradient may be generated from the beginning to the end of the temperature raising process of the final annealing (until reaching the soaking temperature).
  • The temperature gradient can be applied by increasing the temperature such that the furnace has a temperature difference therein, or by heating and/or cooling the coil ends to increase the temperature such that the coil has a temperature difference therein in the final annealing furnace. Regarding the magnitude of the temperature gradient, for example, when the temperature gradient is applied in the width direction of the coil, sensors such as thermocouples are arranged at constant intervals (interval at which temperature gradient can be measured, for example, 100 mm interval) in the width direction to measure the temperature history, so that the temperature gradient of each portion in the steel sheet is calculated. In addition, the minimum value of the temperature gradient throughout (in the entire region of) the coil can be determined by calculating the temperature gradient of each portion.
  • In addition, the temperature gradient varies depending on the size of the furnace, the temperature difference in the furnace, the size and weight of the coil, and the like. In this case, optionally, physical property values such as thermal diffusivity are calculated by using the results of the temperature history at a plurality of portions of the coil actually measured as described above, and then, for example, the furnace wall temperature is provided as a boundary condition, and the temperature gradient of each portion of the coil is calculated by simulation using a known heat transfer calculation software, Fluent (registered trademark), developed by ANSYS, or the like. In the simulation, various conditions are set so that the temperature gradient of each portion of the coil (for example, a range of arbitrary 100 mm intervals in the width direction of the coil) is calculated in consideration of the variation of the temperature gradient. By calculating the temperature gradient of each portion, the minimum value of the temperature gradient throughout the coil can be determined.
  • When there is a difference in the temperature gradient in the radial direction of the coil, sensors such as thermocouples are arranged at constant intervals in the width direction (interval at which a difference in the temperature gradient can be measured, for example, 100 mm interval) at a plurality of locations in the radial direction of the coil, and the temperature history in the width direction of each location is measured, whereby the difference in temperature gradient in the radial direction can be calculated. The minimum value of the temperature gradient throughout the coil can be determined from the temperature gradient calculated at each measurement point in the radial direction of the coil. For example, when a temperature gradient is applied in the width direction of the coil, the temperature history in the radial direction of the coil may be measured at three points or more in total, such that each of the steel sheet located on the outermost side of the coil, the steel sheet located in the radial intermediate portion of the coil, and the steel sheet located on the innermost side of the coil has one or more measurement points in the longitudinal direction of the coil. Similarly, simulation makes it possible to calculate the temperature gradient in the width direction at a plurality of locations in the coil radial direction (for example, each position at intervals of 100 mm in width in the coil radial direction, or each position of the outermost side, the intermediate portion, and the innermost side in the coil radial direction).
  • When the temperature gradient varies in the coil, the temperature gradient tends to be relatively small on the side of the low-temperature end of the coil, and tends to be relatively small at the position on the radially innermost side of the coil. Therefore, the temperature gradient calculated by measurement or simulation at the position that is on the side of the low-temperature end and the radially innermost side of the coil may be determined as the minimum temperature gradient throughout the coil.
    • <Soaking Process>
  • In the soaking process, impurities that adversely affect magnetic properties, such as N, S, and Se, are purified. Therefore, the final annealing temperature (soaking temperature) is preferably 1150 to 1250°C. The annealing time (soaking time) is preferably 10 to 30 hours after the low-temperature side of the temperature gradient of the coil reaches the soaking temperature.
    • [Insulating Coating-Forming Step]
  • The method of manufacturing a grain-oriented electrical steel sheet according to the embodiment may further include an insulating coating-forming step of forming an insulating coating on the surface of the steel sheet. The insulating coating to be formed is not limited, and may be a known coating.
    • [Magnetic Domain Refinement Step]
  • The method of manufacturing a grain-oriented electrical steel sheet according to the embodiment may further include a magnetic domain refinement step of performing magnetic domain refinement on the steel sheet.
  • By performing the magnetic domain refinement treatment, iron loss of the grain-oriented electrical steel sheet can be further reduced.
  • The method of the magnetic domain refinement treatment is not limited. There is a method for narrowing the width of a 180° magnetic domain (performing refinement of a 180° magnetic domain) by forming linear or dotted groove parts extending in a direction intersecting a rolling direction at predetermined intervals in the rolling direction, and a method for narrowing the width of a 180° magnetic domain (performing refinement of a 180° magnetic domain) by forming linear or dotted stress-strain parts or groove parts extending in a direction intersecting a rolling direction at predetermined intervals in the rolling direction.
  • In a case where a stress-strain part is formed, laser beam irradiation, electron beam irradiation, and the like can be applied. In a case where a groove part is formed, a mechanical groove-forming method using a gear or the like, a chemical groove-forming method by electrolytic etching, a thermal groove-forming method by laser irradiation, and the like can be applied.
  • In a case where the insulating coating is damaged due to formation of a stress-strain part or a groove part and characteristics such as insulation properties are deteriorated, the insulating coating may be formed again to repair the damage.
    • Examples <Example 1>
  • By casting, a silicon steel material containing, in terms of mass%, 3.30% of Si, 0.08% of C, 0.027% of acid-soluble Al, 0.008% of N, 0.08% of Mn, 0.02% of S + Se, and a balance of Fe and impurities is obtained.
  • The silicon steel material is heated to 1280 to 1400°C and held for 1 hour, and then hot-rolled to prepare a hot rolled sheet having a sheet thickness of 2.3 mm.
  • Each of the hot rolled sheets except for No. 7 is heated to 1000°C and subjected to annealing (hot-rolled sheet annealing) for 60 seconds.
  • The hot rolled sheet is cold-rolled to a thickness of 0.22 mm to obtain a steel sheet (cold rolled sheet). A sample steel sheet having a length of 200 mm in the rolling direction and a length of 600 mm in the width direction is cut out from the steel sheet.
  • Thereafter, the sample steel sheet is subjected to decarburization annealing in which the sample steel sheet is held at 750 to 900°C for 100 seconds, and the primary recrystallization grain size is controlled to be 5 to 20 µm. (The primary recrystallization grain size is measured after the decarburization annealing step and before the final annealing.) In addition, nitriding treatment is performed at least in one timing of: during the temperature raising process and soaking process in the decarburization annealing step; between the decarburization annealing step and the final annealing step; and during the temperature raising process in the final annealing step and before the start of the secondary recrystallization, and the nitrogen amount after the final nitriding treatment step is controlled to be 160 to 380 ppm. In the table, for example, "Between decarburization annealing step and final annealing step" means that nitriding treatment is performed one time "between the completion of the decarburization annealing step and the start of the final annealing step", and "Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization" means that nitriding treatment is performed two times, "between the completion of the decarburization annealing step and the start of the final annealing step" and "from the start of the final annealing step to the start of the secondary recrystallization in the temperature raising process in the final annealing step".
  • After the decarburization annealing, the steel sheet is applied with an annealing separator containing MgO as a main component, and then subjected to final annealing such that the steel sheet end has a high temperature, and a temperature gradient of 0 to 5.0 °C/cm is applied to the entire region in the direction perpendicular to the rolling direction (width direction) to generate secondary recrystallization. The average temperature rising rate from the start of the secondary recrystallization to the completion of the secondary recrystallization in the boundary region is 10 °C/hr, the final annealing temperature is 1200°C, and the soaking time is 30 hours.
  • The temperature gradient is uniformly applied throughout the sample steel sheet. The temperature gradient is applied by increasing the temperature such that the furnace has a temperature difference therein. The magnitude of the temperature gradient is controlled by raising the temperature while measuring the temperature at intervals of 100 mm in the width direction of the steel sheet.
  • A sample of 60 mm in the width direction and 200 mm in the rolling direction is collected from the obtained steel sheet, and magnetic properties this sample is measured by the SST method (see JISC2556:2015 Annex JA) to measure the magnetic flux density B8 in the rolling direction.
  • Tables 1-1 to 1-3 show the results. [Table 1-1]
    Sample No. Hot rolling step Hot-rolled sheet annealing step Decarburization annealing step Nitriding treatment step Final annealing step Magnetic flux density B8 (T) Note
    Temperature raising process
    Heating temperature (°C) Annealing temperature (°C) Holding time (sec) Annealing temperature (°C) Holding time (sec) Primary recrystallization grain size (µm) Performing timing Nitrogen amount after nitriding treatment (ppm) Temperature gradient (°C/cm)
    1 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 1.5 1.956 Inventive Example
    2 1350 1000 60 750 100 10 During decarburization annealing step 210 1.5 1.956 Inventive Example
    3 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 1.5 1.956 Inventive Example
    4 1350 1000 60 750 100 10 During decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 1.5 1.956 Inventive Example
    5 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; during decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 1.5 1.956 Inventive Example
    6 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; and during decarburization annealing step 210 1.5 1.956 Inventive Example
    7 1350 - - 750 100 10 Between decarburization annealing step and final annealing step 210 1.5 1.600 Comparative Example
    8 1280 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 1.5 1.800 Comparative Example
    9 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step 210 0.0 1.920 Comparative Example
    10 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step 210 0.5 1.947 Inventive Example
    11 1310 1000 60 700 100 5 During decarburization annealing step 210 0.5 1.947 Inventive Example
    12 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.947 Inventive Example
    13 1310 1000 60 700 100 5 During decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.947 Inventive Example
    14 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step; during decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.947 Inventive Example
    15 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step; and during decarburization annealing step 210 0.5 1.947 Inventive Example
    16 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step 210 1.0 1.954 Inventive Example
    [Table 1-2]
    Sample No. Hot rolling step Hot-rolled sheet annealing step Decarburization annealing step Nitriding treatment step Final annealing step Magnetic flux density B8 (T) Note
    Temperature raising process
    Heating temperature (°C) Annealing temperature (°C) Holding time (sec) Annealing temperature (°C) Holding time (sec) Primary recrystallization grain size (µm) Performing timing Nitrogen amount after nitriding treatment (ppm) Temperature gradient (°C/cm)
    17 1310 1000 60 700 100 5 Between decarburization annealing step and final annealing step 210 1.5 1.957 Inventive Example
    18 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 0.0 1.920 Comparative Example
    19 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 0.5 1.945 Inventive Example
    20 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 1.0 1.952 Inventive Example
    21 1400 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 1.5 1.956 Inventive Example
    22 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 0.0 1.920 Comparative Example
    23 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 0.5 1.940 Inventive Example
    24 1350 1000 60 800 100 15 During decarburization annealing step 210 0.5 1.940 Inventive Example
    25 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.940 Inventive Example
    26 1350 1000 60 800 100 15 During decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.940 Inventive Example
    27 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step; during decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.5 1.940 Inventive Example
    28 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step; and during decarburization annealing step 210 0.5 1.940 Inventive Example
    29 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 1.0 1.948 Inventive Example
    30 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 1.5 1.953 Inventive Example
    31 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 2.0 1.956 Inventive Example
    32 1350 1000 60 800 100 15 Between decarburization annealing step and final annealing step 210 5.0 1.959 Inventive Example
    33 1350 1000 60 850 100 20 Between decarburization annealing step and final annealing step 210 0.0 1.920 Comparative Example
    34 1350 1000 60 850 100 20 Between decarburization annealing step and final annealing step 210 0.5 1.923 Comparative Example
    35 1350 1000 60 850 100 20 Between decarburization annealing step and final annealing step 210 1.0 1.930 Comparative Example
    36 1350 1000 60 850 100 20 Between decarburization annealing step and final annealing step 210 1.5 1.937 Comparative Example
    37 1350 1000 60 750 100 10 Between decarburization annealing step and final annealine step 160 0.0 1.920 Comparative Example
    [Table 1-3]
    Sample No. Hot rolling step Hot-rolled sheet annealing step Decarburization annealing step Nitriding treatment step Final annealing step Magnetic flux density B8 (T) Note
    Temperature raising process
    Heating temperature (°C) Annealing temperature (°C) Holding time (sec) Annealing temperature (°C) Holding time (sec) Primary recrystallization grain size (µm) Performing timing Nitrogen amount after nitriding treatment (ppm) Temperature gradient (°C/cm)
    38 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 0.5 1.925 Comparative Example
    39 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 1.0 1.932 Comparative Example
    40 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 160 1.5 1.938 Comparative Example
    41 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 300 0.0 1.920 Comparative Example
    42 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 300 0.5 1.949 Inventive Example
    43 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 300 1.0 1.955 Inventive Example
    44 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 300 1.5 1.957 Inventive Example
    45 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 350 0.0 1.920 Comparative Example
    46 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 350 0.5 1.950 Inventive Example
    47 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 350 1.0 1.956 Inventive Example
    48 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 350 1.5 1.957 Inventive Example
    49 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 380 0.0 1.920 Comparative Example
    50 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 380 0.5 1.950 Inventive Example
    51 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 380 1.0 1.956 Inventive Example
    52 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 380 1.5 1.957 Inventive Example
    53 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step 210 0.4 1.939 Comparative Example
    54 1350 1000 60 750 100 10 During decarburization annealing step 210 0.4 1.939 Comparative Example
    55 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.4 1.939 Comparative Example
    56 1350 1000 60 750 100 10 During decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.4 1.939 Comparative Example
    57 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; during decarburization annealing step; and during temperature raising process in final annealing step and before start of secondary recrystallization 210 0.4 1.939 Comparative Example
    58 1350 1000 60 750 100 10 Between decarburization annealing step and final annealing step; and during decarburization annealing step 210 0.4 1.939 Comparative Example
  • As can be seen from Tables 1-1 to 1-3, when the temperature gradient is within the range of 0.5 °C/cm or more in the final annealing, the nitrogen amount after the nitriding treatment is 210 ppm or more regardless of the number of times and the timing of the nitriding treatment, and the primary recrystallization grain size is 15 µm or less, a high magnetic flux density (magnetic flux density B8 is 1.940 T or more) can be achieved.
    • <Example 2>
  • A silicon steel material (slab) having a chemical composition shown in Table 2 (unit: mass%, balance: Fe and impurities) is obtained by casting.
  • The silicon steel material is heated to 1350°C and held for 1 hour, and then hot-rolled to prepare a hot rolled sheet having a sheet thickness of 2.3 mm.
  • The hot rolled sheet is held at an annealing temperature of 950 to 1100°C for 30 to 120 seconds for hot-rolled sheet annealing.
  • The hot rolled sheet after the hot rolled sheet annealing is cold-rolled to a thickness of 0.22 mm to obtain a steel sheet (cold rolled sheet). A sample steel sheet having a length of 200 mm in the rolling direction and a length of 600 mm in the width direction is cut out from the steel sheet.
  • Thereafter, the sample steel sheet is subjected to decarburization annealing, and the primary recrystallization grain size is controlled to be 10 µm. As the decarburization annealing conditions, the annealing temperature is 750 to 800°C, and the holding time is 50 to 200 seconds. Nitriding treatment is performed between the decarburization annealing step and the final annealing step, and the nitrogen amount is controlled to be 210 ppm. The nitriding treatment is performed one time between the completion of the decarburization annealing step and the start of the final annealing step.
  • After the decarburization annealing, the steel sheet is applied with an annealing separator containing MgO as a main component, and then subjected to final annealing such that the steel sheet end has a high temperature, and a temperature gradient of 0.5 °C/cm is applied to the entire region in the direction perpendicular to the rolling direction (width direction) to generate secondary recrystallization. The final annealing temperature is 1150 to 1250°C, and the soaking time is 10 to 30 hours. The temperature gradient is uniformly applied throughout the sample steel sheet. The temperature gradient is applied by increasing the temperature such that the furnace has a temperature difference therein. The magnitude of the temperature gradient is controlled by raising the temperature while measuring the temperature at intervals of 100 mm in the width direction of the steel sheet.
  • A sample of 60 mm in the width direction and 200 mm in the rolling direction is collected from the obtained steel sheet, and magnetic properties of this sample is measured by the SST method (see JISC2556:2015 Annex JA) to measure the magnetic flux density B8 in the rolling direction.
  • Table 2 shows the results. [Table 2]
    Sample No Chemical composition (mass%) balance : Fe and impurities Magnetic flux density B8 (T) Note
    Si C sol.Al N Mn S+Se Cr Cu P Ni
    59 3.30 0.08 0.027 0.008 0.08 0.02 - - - - 1.945 Inventive Example
    60 2.70 0.06 0.027 0.008 0.08 0.02 - - - - 1.950 Inventive Example
    61 4.00 0.12 0.027 0.008 0.08 0.02 - - - - 1.940 Inventive Example
    62 4.80 0.14 0.027 0.008 0.08 0.02 - - - - 1.940 Inventive Example
    63 2.70 0.03 0.027 0.008 0.08 0.02 - - - - 1.946 Inventive Example
    64 3.80 0.15 0.027 0.008 0.08 0.02 - - - - 1.942 Inventive Example
    65 3.30 0.08 0.015 0.004 0.08 0.02 - - - - 1.940 Inventive Example
    66 3.30 0.08 0.020 0.006 0.08 0.02 - - - - 1.943 Inventive Example
    67 3.30 0.08 0.040 0.012 0.08 0.02 - - - - 1.941 Inventive Example
    68 3.20 0.08 0.027 0.008 0.25 0.05 - - - - 1.945 Inventive Example
    69 3.00 0.08 0.027 0.008 0.40 0.05 - - - - 1.944 Inventive Example
    70 3.20 0.08 0.027 0.008 0.04 0.01 - - - - 1.944 Inventive Example
    71 3.30 0.08 0.027 0.008 0.08 0.02 0.15 - - - 1.945 Inventive Example
    72 3.10 0.05 0.027 0.008 0.08 0.02 0.25 - - - 1.943 Inventive Example
    73 3.30 0.08 0.027 0.008 0.08 0.02 - 0.2 - - 1.944 Inventive Example
    74 3.10 0.08 0.027 0.008 0.08 0.02 - 0.4 - - 1.943 Inventive Example
    75 3.20 0.08 0.027 0.008 0.08 0.02 - - 0.2 - 1.943 Inventive Example
    76 3.20 0.08 0.027 0.008 0.08 0.02 - - 0.4 - 1.941 Inventive Example
    77 3.20 0.08 0.027 0.008 0.08 0.02 - - - 0.20 1.943 Inventive Example
    78 3.00 0.08 0.027 0.008 0.08 0.02 - - - 0.75 1.940 Inventive Example
  • As can be seen from Table 2, an excellent magnetic flux density B8 is obtained in all of the chemical compositions.
    • INDUSTRIAL APPLICABILITY
  • According to the present invention, it is possible to provide a method of manufacturing a grain-oriented electrical steel sheet in which final annealing is performed while applying a temperature gradient in the boundary region between the primary recrystallization region and the secondary recrystallization region to manufacture a grain-oriented electrical steel sheet having a high magnetic flux density, the method being a method of manufacturing a grain-oriented electrical steel sheet capable of obtaining a sufficient magnetic flux density improving effect even under a small temperature gradient. Therefore, the present invention has high industrial applicability.

Claims (2)

  1. A method of manufacturing a grain-oriented electrical steel sheet, the method comprising:
    a hot rolling step of heating a silicon steel material containing, in terms of mass%, 0.80 to 7.00% of Si to a temperature of higher than 1300°C and hot rolling the silicon steel material, to obtain a hot rolled sheet;
    a hot-rolled sheet annealing step of annealing the hot rolled sheet;
    a cold rolling step of cold-rolling the hot rolled sheet after the hot rolling step or after the hot-rolled sheet annealing step to obtain a steel sheet having a final sheet thickness;
    a decarburization annealing step of decarburization-annealing the steel sheet after the cold rolling step to obtain a steel sheet having a primary recrystallization grain size of 15 µm or less;
    an annealing separator applying step of applying an annealing separator on the steel sheet after the decarburization annealing step and coiling the steel sheet into a coil shape;
    a nitriding treatment step of increasing a nitrogen amount in the steel sheet; and
    a final annealing step of final-annealing the steel sheet coiled into a coil shape,
    wherein the final annealing step has a temperature raising process and a soaking process, and a temperature gradient of 0.5 °C/cm or more is generated in a boundary region between a primary recrystallization region and a secondary recrystallization region at least in one period from the start of secondary recrystallization to completion of the secondary recrystallization in the temperature raising process; and
    the nitriding treatment step is performed by annealing in an atmosphere containing a gas having nitriding ability at least in one stage of: during the decarburization annealing step; between the decarburization annealing step and the final annealing step; and during the temperature raising process in the final annealing step and before the start of the secondary recrystallization, so that the nitrogen amount in the steel sheet is 210 ppm or more based on mass after the nitriding treatment step.
  2. The method of manufacturing a grain-oriented electrical steel sheet according to claim 1, wherein
    the silicon steel material includes, as a chemical composition, in terms of mass%, 0.80 to 7.00% of Si, 0.15% or less of C, 0.010 to 0.065% of acid-soluble Al, 0.004 to 0.012% of N, 0.01 to 0.50% of Mn, 0.01 to 0.05% in total of S and Se, 0 to 0.30% of Cr, 0 to 0.4% of Cu, 0 to 0.5% of P, 0 to 1.00% of Ni, and a balance of Fe and impurities.
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