WO2024214818A1 - 方向性電磁鋼板および絶縁被膜の形成方法 - Google Patents

方向性電磁鋼板および絶縁被膜の形成方法 Download PDF

Info

Publication number
WO2024214818A1
WO2024214818A1 PCT/JP2024/014841 JP2024014841W WO2024214818A1 WO 2024214818 A1 WO2024214818 A1 WO 2024214818A1 JP 2024014841 W JP2024014841 W JP 2024014841W WO 2024214818 A1 WO2024214818 A1 WO 2024214818A1
Authority
WO
WIPO (PCT)
Prior art keywords
steel sheet
grain
ion concentration
coating
oriented electrical
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.)
Ceased
Application number
PCT/JP2024/014841
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
和年 竹田
真介 高谷
隆史 片岡
勇樹 小ケ倉
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
Priority to CN202480024429.6A priority Critical patent/CN120958172A/zh
Priority to KR1020257034143A priority patent/KR20250163937A/ko
Priority to JP2025514033A priority patent/JPWO2024214818A1/ja
Priority to EP24788840.7A priority patent/EP4696809A1/en
Publication of WO2024214818A1 publication Critical patent/WO2024214818A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • 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
    • 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
    • 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
    • C21D8/1288—Application of a tension-inducing 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
    • 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
    • C21D8/1294—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 localised treatment
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22C38/16—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
    • C22C38/60—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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/20—Orthophosphates containing aluminium cations
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/22—Orthophosphates containing alkaline earth metal cations
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/083—Iron or steel solutions containing H3PO4
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
    • H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
    • 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 grain-oriented electrical steel sheet and a method for forming an insulating coating.
  • Grain-oriented electrical steel sheets are primarily used in transformers. Transformers are continuously excited over a long period of time, from installation to disposal, and continue to generate energy loss. For this reason, the energy loss that occurs when magnetized with alternating current, i.e., iron loss, is the primary indicator that determines the performance of a transformer.
  • a forsterite-based coating with excellent coating adhesion is produced during the finish annealing process of electrical steel sheets by a reaction between oxides on the surface of the steel sheet and an annealing separator, and is a coating that can apply tension to steel sheets.
  • the method disclosed in Patent Document 1 in which a coating liquid mainly composed of colloidal silica and phosphate is baked onto the surface of a steel sheet to form an insulating coating, is an effective method for reducing iron loss because it is highly effective in applying tension to the steel sheet. Therefore, the general method for manufacturing grain-oriented electrical steel sheets is to leave the forsterite-based coating formed in the final annealing process and apply an insulating coating mainly composed of phosphate on top of it.
  • Patent Document 2 discloses a technique for preventing the formation of inorganic coatings, in which the steel sheet surface is made mirror-finished by chemical polishing or electrolytic polishing after pickling to remove surface deposits following normal finish annealing. It has been found that an even more excellent iron loss improvement effect can be obtained by forming a tensioned insulating coating on the surface of an inorganic coating-free oriented electrical steel sheet obtained by such a known method. Furthermore, in addition to improving iron loss, tensioned insulating coatings can also impart various other properties such as corrosion resistance, heat resistance, and slipperiness.
  • inorganic coatings not only have the effect of providing insulation, but also have the effect of serving as an intermediate layer that ensures adhesion when forming a tension coating (tension-applying insulating coating).
  • inorganic coatings are formed in a state in which they penetrate deeply into the steel sheet, and therefore have excellent adhesion to the metal steel sheet. Therefore, when a tension-applying coating (tension coating) whose main components are colloidal silica or phosphate is formed on the surface of an inorganic coating, the coating has excellent adhesion.
  • Patent Document 3 discloses a technique in which a grain-oriented electrical steel sheet having no inorganic coating is annealed in a weakly reducing atmosphere to selectively thermally oxidize silicon inevitably contained in the silicon steel sheet, thereby forming an SiO2 layer on the steel sheet surface, and then a tension-imparting insulating coating is formed.
  • Patent Document 4 discloses a technique in which a grain-oriented electrical steel sheet having no inorganic coating is anodically electrolyzed in a silicate aqueous solution to form an SiO2 layer on the steel sheet surface, and then a tension-imparting insulating coating is formed.
  • Patent Document 3 requires preparation of an annealing facility capable of controlling the atmosphere in order to perform annealing in a weakly reducing atmosphere, which causes a problem in terms of processing costs.
  • annealing facility capable of controlling the atmosphere in order to perform annealing in a weakly reducing atmosphere, which causes a problem in terms of processing costs.
  • Patent Document 4 in order to obtain a SiO 2 layer on the steel sheet surface that maintains sufficient adhesion to the tension-imparting insulating coating by performing anodizing in a silicate aqueous solution, it is necessary to prepare a new electrolytic processing facility, which causes a problem in terms of processing costs.
  • Patent Document 5 discloses a grain-oriented electrical steel sheet having a base steel sheet and an insulating coating formed on the surface of the base steel sheet, the insulating coating being formed on the base steel sheet side, an intermediate layer containing a crystalline metal phosphate, and a tensile coating layer formed on the surface side of the insulating coating.
  • the intermediate layer can be formed by chemical conversion treatment.
  • Patent Document 6 relates to a method for producing a grain-oriented silicon steel sheet, and discloses a method in which, prior to the formation of a tension-imparting insulating coating, a coating mainly made of zinc phosphate is formed on a grain-oriented silicon steel sheet that has been subjected to secondary recrystallization in an amount of 0.1 g/ m2 or more and 10 g/ m2 or less per side of the steel sheet.
  • the present invention aims to provide a method for forming a grain-oriented electrical steel sheet and insulating coating that has excellent adhesion and magnetic properties of the tensile coating and does not reduce the space factor of the transformer (core).
  • the inventors discovered that when providing a layer containing a metal phosphate as an intermediate layer to improve adhesion between the base steel sheet and the tensile coating layer, the interface between the intermediate layer and the base material can be smoothed by adjusting the ratio of metal ions, phosphate ions, and nitrate ions in the chemical conversion treatment solution within a specific range, resulting in a grain-oriented electrical steel sheet that has excellent adhesion and magnetic properties of the tensile coating and does not reduce the space factor of the transformer (core).
  • the present invention was made in consideration of the above findings.
  • the gist of one aspect of the present invention is as follows.
  • a grain-oriented electrical steel sheet comprises a base steel sheet, An insulating coating formed on a surface of the base steel sheet; having The insulating coating is An intermediate layer formed on the base steel sheet side and containing a crystalline metal phosphate; a tensile coating layer formed on a surface side of the insulating coating, When the interface between the base steel plate and the intermediate layer is observed at 5000 times magnification by a scanning electron microscope in a cross section along the thickness direction of the intermediate layer, the ratio of the interface length L to the observed image width W is 100.0 to 120.0%.
  • the tensile coating layer may contain a metal phosphate and silica.
  • a method for forming an insulating coating according to one aspect of the present invention is a method for forming the insulating coating provided on the grain-oriented electrical steel sheet according to the above-mentioned [1], comprising the steps of: a finish annealing process in which an annealing separator containing 10 to 100 mass% of Al 2 O 3 is applied to a steel sheet, the steel sheet is dried, and then finish annealing is performed; an annealing separator removing step of removing excess annealing separator from the steel sheet after the finish annealing step; a pickling process in which the steel sheet after the annealing separator removal process is pickled with 0.1 to 5 mass % of one inorganic acid selected from sulfuric acid, chloric acid, nitric acid, and phosphoric acid for 1 to 20 seconds; an immersion step of immersing the steel sheet after the pickling step in a treatment solution containing a metal phosphate, an oxidizing agent, and iron ions; a drying step of
  • the steel sheet after the pickling step may be immersed in the treatment liquid having a liquid temperature of 20 to 85° C. for 2 to 60 seconds.
  • the nitrate ion concentration may be 2.0 to 25.0 g/L.
  • a directional electromagnetic steel sheet and a method for forming an insulating coating that have excellent adhesion and magnetic properties of the tensile coating and do not reduce the space factor of the transformer (core).
  • FIG. 1 is an example of a cross-sectional view of a grain-oriented electrical steel sheet according to an embodiment of the present invention.
  • FIG. 11 is a schematic diagram for explaining a method for determining a concavo-convex index according to the present embodiment.
  • a grain-oriented electrical steel sheet according to one embodiment of the present invention (grain-oriented electrical steel sheet according to this embodiment) and a method for manufacturing the grain-oriented electrical steel sheet according to this embodiment, including a method for forming the insulating coating provided on the grain-oriented electrical steel sheet according to this embodiment, will be described.
  • the grain-oriented electrical steel sheet according to this embodiment will be described.
  • the grain-oriented electrical steel sheet 100 has a base steel sheet 1 and an insulating coating 2 formed on the surface of the base steel sheet 1.
  • the grain-oriented electrical steel sheet 100 according to this embodiment does not substantially have a forsterite-based coating on the surface of the base steel sheet 1.
  • a forsterite-based coating is not intentionally formed on the surface of the base steel sheet 1, but the presence of a forsterite-based coating is permitted as long as the coating amount of the forsterite-based coating is 1 g/ m2 or less (in that case, it is present in a part between the base steel sheet 1 and the insulating coating 2).
  • the grain-oriented electrical steel sheet 100 according to this embodiment may have a forsterite-based coating of 0 to 1 g/ m2 on the surface of the base steel sheet 1.
  • the insulating coating 2 has a tensile coating layer 22 formed on the surface side of the insulating coating 2 (i.e., the surface side of the directional electromagnetic steel sheet 100) and an intermediate layer 21 formed on the base steel sheet 1 side and containing a crystalline metal phosphate.
  • the ratio of the interface length L to the observed image width W (irregularity index) of the intermediate layer 21 is 100 to 120%.
  • the grain-oriented electrical steel sheet 100 is significantly characterized by the structure of the insulating coating 2 formed on the surface of the base steel sheet 1, and the base steel sheet 1 included in the grain-oriented electrical steel sheet 100 is not limited in terms of its chemical composition. However, in order to obtain the characteristics generally required of a grain-oriented electrical steel sheet, it is preferable that the chemical components contain the following: In this embodiment, % relating to the chemical components is % by mass unless otherwise specified.
  • C 0.010% or less
  • C (carbon) is an element effective for controlling the structure of the steel sheet in the process up to the completion of the decarburization annealing process in the manufacturing process.
  • the C content is preferably 0.010% or less.
  • the C content is more preferably 0.005% or less. The lower the C content, the more preferable it is, but even if the C content is reduced to less than 0.0001%, the effect of grain control is saturated and the manufacturing cost is only increased. Therefore, the C content may be 0.0001% or more.
  • Si 2.50-4.00%
  • Silicon (Si) is an element that increases the electrical resistance of grain-oriented electrical steel sheets and improves their core loss characteristics. If the Si content is less than 2.50%, a sufficient effect of reducing eddy current loss cannot be obtained. Therefore, the Si content is preferably 2.50% or more, more preferably 2.70% or more, and further preferably 3.00% or more. On the other hand, if the Si content exceeds 4.00%, the grain-oriented electrical steel sheet becomes embrittled and the sheet passing property is significantly deteriorated. In addition, the workability of the grain-oriented electrical steel sheet is deteriorated, and the steel sheet is likely to break during rolling. For this reason, the Si content is preferably 4.00% or less, more preferably 3.80% or less, and further preferably 3.70% or less.
  • Mn 0.01-0.50%
  • Mn manganese
  • Mn is an element that combines with S to form MnS during the manufacturing process. This precipitate acts as an inhibitor (a suppressor of normal grain growth) and suppresses secondary recrystallization in steel.
  • Mn is an element that also improves the hot workability of steel. If the Mn content is less than 0.01%, the above effects cannot be sufficiently obtained. Therefore, the Mn content is preferably 0.01% or more, and more preferably 0.02% or more. On the other hand, if the Mn content exceeds 0.50%, secondary recrystallization does not occur, and the magnetic properties of the steel deteriorate.
  • the Mn content is preferably 0.50% or less, more preferably 0.20% or less, and further preferably 0.10% or less.
  • N 0.010% or less
  • N nitrogen
  • the N content is preferably 0.010% or less.
  • the N content is more preferably 0.008% or less.
  • the lower limit of the N content is not particularly specified, but reducing the N content to less than 0.001% would only increase the manufacturing cost, and therefore the N content may be set to 0.001% or more.
  • Sol. Al 0.020% or less
  • Sol. Al (acid-soluble aluminum) is an element that combines with N to form AlN, which functions as an inhibitor, during the manufacturing process of the grain-oriented electrical steel sheet.
  • the sol. Al content is preferably 0.020% or less.
  • the sol. Al content is more preferably 0.010% or less, and further preferably less than 0.001%.
  • the lower limit of the sol. Al content is not particularly specified, but even if it is reduced to less than 0.0001%, the manufacturing cost will only increase. Therefore, the sol. Al content may be 0.0001% or more.
  • S 0.010% or less
  • S (sulfur) is an element that combines with Mn in the manufacturing process to form MnS, which functions as an inhibitor.
  • the S content is preferably 0.010% or less. It is more preferable that the S content in the grain-oriented electrical steel sheet is as low as possible. For example, it is less than 0.001%. However, even if the S content in the grain-oriented electrical steel sheet is reduced to less than 0.0001%, the manufacturing cost will only increase. Therefore, the S content in the grain-oriented electrical steel sheet may be 0.0001% or more.
  • the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment may contain the above-mentioned elements, with the balance being Fe and impurities.
  • Sn, Cu, Se, and Sb may also be contained in the ranges shown below.
  • W, Nb, Ti, Ni, Co, V, Cr, and Mo are contained in a total of 1.0% or less, this does not impair the effect of the grain-oriented electrical steel sheet according to this embodiment.
  • impurities refer to elements that are mixed in from raw materials such as ore, scrap, or the manufacturing environment when the base steel sheet is industrially manufactured, and are permissible to be contained in amounts that do not adversely affect the function of the grain-oriented electrical steel sheet according to this embodiment.
  • Sn 0-0.50%
  • Sn (tin) is an element that contributes to improving magnetic properties through controlling the primary crystal structure.
  • the Sn content is preferably 0.01% or more.
  • Sn Content is more preferably 0.02% or more, and further preferably 0.03% or more.
  • the Sn content is preferably 0.50% or less.
  • the amount is more preferably 0.30% or less, and further preferably 0.10% or less.
  • Cu 0-0.50%
  • Cu (copper) is an element that contributes to an increase in the Goss orientation occupancy rate in the secondary recrystallized structure.
  • the Cu content is 0.01% or more.
  • the amount is more preferably 0.02% or more, and further preferably 0.03% or more.
  • the Cu content exceeds 0.50%, the steel sheet becomes embrittled during hot rolling.
  • the Cu content is preferably 50% or less, more preferably 0.30% or less, and further preferably 0.10% or less.
  • Se is an element that has a magnetic property improving effect.
  • Se content is 0.001% or more in order to effectively exhibit the magnetic property improving effect.
  • Se The content is more preferably 0.003% or more, and further preferably 0.006% or more.
  • the Se content is preferably 0.020% or less.
  • the Se content is more preferably 0.015% or less. % or less, and more preferably 0.010% or less.
  • Sb 0-0.50%
  • Sb (antimony) is an element that has a magnetic property improving effect.
  • the Sb content is preferably 0.005% or more in order to effectively exhibit the magnetic property improving effect.
  • the content is more preferably 0.01% or more, and further preferably 0.02% or more.
  • the Sb content is preferably 0.50% or less.
  • the Sb content is more preferably 0. .30% or less, and more preferably 0.10% or less.
  • the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet contains the above-mentioned elements, with the remainder being Fe and impurities.
  • the chemical composition of the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment can be measured using the known ICP atomic emission spectroscopy.
  • an insulating coating is formed on the surface, it must be peeled off before measurement.
  • the peeling method involves immersing the sheet in a high-concentration alkaline solution (e.g., a 30% sodium hydroxide solution heated to 85°C) for 20 minutes or more, which can result in the coating being peeled off. Peeling can be determined visually. In the case of small samples, the coating may also be peeled off by surface grinding.
  • the grain-oriented electrical steel sheet 100 has an insulating coating 2 formed on the surface of a base steel sheet 1 .
  • the insulating coating 2 has a structure in which an intermediate layer 21 and a tensile coating layer 22 are laminated in this order from the base steel sheet 1 side.
  • grain-oriented electrical steel sheets generally have a forsterite-based coating formed in the final annealing process and an insulating coating (tensile insulating coating) formed thereon.
  • a forsterite-based coating hinders the movement of domain walls and has a negative effect on iron loss, and thus grain-oriented electrical steel sheets without a forsterite-based coating have been studied in order to further improve magnetic properties.
  • an intermediate layer 21 containing crystalline metal phosphate is formed between the base steel sheet 1 and the tensile coating layer 2, thereby improving the adhesion between the base steel sheet 1 and the tensile coating layer 22 via the intermediate layer 21.
  • the intermediate layer 21 contains crystalline metal phosphate
  • the tensile coating formed thereon (which becomes the tensile coating layer 22 after formation) also contains metal phosphate, resulting in high affinity and excellent adhesion between the intermediate layer and the tensile coating layer.
  • the intermediate layer 1 when the intermediate layer 1 is formed by immersing in a treatment liquid containing metal phosphate, as described below, it can be formed on the surface of the base steel sheet 1 by utilizing a chemical reaction, and adhesion between the intermediate layer 21 and the base steel sheet 1 can also be ensured.
  • the intermediate layer 21 does not contain a crystalline metal phosphate, the above-mentioned effect cannot be obtained.
  • the ratio of the crystalline metal phosphate in the intermediate layer 21 is preferably 80 mass % or more, and may be 100 mass %. In terms of adhesion, it is preferable to use one of zinc phosphate, manganese phosphate, zinc calcium phosphate, and iron manganese phosphate as the metal phosphate.
  • the intermediate layer 21 may contain oxides and elements such as Fe and Si diffused from the base steel sheet 1 as the remainder of the metal phosphate.
  • the cause of the deterioration of the magnetic properties is that when the intermediate layer is formed, i.e., during chemical conversion treatment, the surface of the base steel sheet is etched at the same time as the phosphate crystals are precipitated, forming an uneven structure at the interface between the base steel sheet and the intermediate layer, which results in the obstruction of the flow of magnetic flux through the base steel sheet.
  • the unevenness index also affects the space factor.
  • the unevenness index increases because the chemical conversion treatment liquid used to form the intermediate layer etches the surface of the steel sheet, but at the same time, the fine unevenness on the surface side of the intermediate layer 21 also increases. As a result, the fine unevenness of the tensile coating layer 22 formed above the intermediate layer 21 also increases, resulting in a decrease in the space factor.
  • the degree of unevenness (irregularity level) at the interface between the base steel sheet 1 and the intermediate layer 21 is reduced, thereby ensuring good adhesion and space factor while suppressing deterioration of the magnetic properties.
  • L/W which is the ratio of the interface length L to the observed image width W (irregularity index)
  • FIG. 2 is a schematic diagram for explaining how to determine the unevenness index L/W, and is a schematic cross-sectional diagram taken along the thickness direction of the intermediate layer 21.
  • the cross section is observed at 5000 times magnification by SEM to obtain an observation image including the interface between the base steel sheet 1 and the intermediate layer 21.
  • the distance between two points of the interface between the base steel sheet 1 and the intermediate layer 21 in the observation image is set as the observation image width W
  • the actual interface path i.e., the curved path tracing the actual interface
  • the interface length L the unevenness index L/W (%) is obtained.
  • This unevenness index L/W is an index of the degree of unevenness of the interface, and it can be said that the smaller the unevenness index L/W, the smaller the degree of unevenness and the better the smoothing of the interface.
  • the degree of unevenness observed changes depending on the observation magnification by SEM. Therefore, the observation magnification by SEM is set to a range suitable for observing the interface, and is set to 5000 times in this embodiment.
  • the cross section from which the observation image for measuring the unevenness index L/W is obtained is selected from a flat portion on the surface of the grain-oriented electrical steel sheet that has no surface defects or fine processing, and when calculating the unevenness index L/W, the average value of the numerical values measured from the observation images at three points is used.
  • the observed image width W and interface length L can be easily determined by using an application system such as "LUZEX AP" manufactured by Nireco Corporation for cross-sectional images taken with an electron microscope.
  • the unevenness index L/W is 100.0 to 120.0%. If the unevenness index L/W exceeds 120.0%, the degree of unevenness at the interface increases, and there is a risk of the magnetic properties deteriorating. Therefore, the unevenness index is 120.0% or less. It is preferably less than 120.0%, more preferably 118.0% or less, even more preferably 115.0% or less, and even more preferably 110.0% or less.
  • the lower limit of the unevenness index L/W is 100.0%. When the unevenness index L/W is 100.0%, the observed image width W and the interface length L are the same, that is, the degree of unevenness is zero and the interface is smooth.
  • the thickness of the intermediate layer 21 is preferably 1.0 to 9.0 ⁇ m. If the average thickness of the intermediate layer 21 is less than 1.0 ⁇ m, the effect of improving the adhesion between the base steel sheet 1 and the insulating coating 2 via the intermediate layer 21 may not be sufficiently obtained. On the other hand, if the average thickness of the intermediate layer 21 exceeds 9.0 ⁇ m, the magnetic properties may deteriorate.
  • the thickness of the intermediate layer 21 can be determined by the following method.
  • the thickness of the intermediate layer 21 can be obtained by measurement using a scanning electron microscope (SEM) and an energy dispersive elemental analyzer. That is, a sample consisting of the base steel sheet 1 and the insulating coating layer 2 is cut, and the polished cross section is observed with a scanning electron microscope at 5000 times magnification to measure the thickness of the insulating coating layer 2.
  • the thickness of the intermediate layer 21 can be obtained by calculation using the energy dispersive elemental analyzer, with the portion of the insulating coating layer 2 that contains Si being the tensile coating layer 22 and the portion that does not contain Si being the intermediate layer 21. Measurements are made at five or more points, and the average is taken as the thickness of the intermediate layer 21.
  • the intermediate layer 21 is formed at a different time from the tensile coating layer 22 formed on top of it, but both the intermediate layer 21 and the tensile coating layer 22 function as the insulating coating 2.
  • the mass proportion of the crystalline metal phosphate in the intermediate layer 21 and the type of the metal phosphate can be determined by measuring a cross section along the thickness direction of the intermediate layer 21 using a scanning electron microscope (SEM) and an energy dispersive elemental analyzer. Whether the metal phosphate in the intermediate layer 21 is a crystalline metal phosphate can be determined by X-ray crystal structure analysis.
  • the base steel plate 1 and the insulating coating 2 can be distinguished by the presence or absence of phosphorus.
  • the intermediate layer 21 and the tensile coating layer 22 can be distinguished by the presence or absence of silicon.
  • a tensile coating is formed on the surface of the intermediate layer 21 , so that a tensile coating layer 22 is provided on the surface side of the insulating coating 2 .
  • the tensile coating layer 22 is not particularly limited as long as it is used as an insulating coating for a grain-oriented electrical steel sheet, but it preferably contains a metal phosphate from the viewpoint of adhesion to the intermediate layer 21 (adhesion to the base steel sheet 1 via the intermediate layer 21).
  • the tensile coating layer 22 has a composition mainly composed of aluminum phosphate and silica.
  • the tensile coating layer 22 preferably contains metal phosphate and silica (derived from colloidal silica in the coating liquid) so that the silica content is 20.0% by mass or more.
  • metal phosphate and silica derived from colloidal silica in the coating liquid
  • the silica content of the tensile coating layer 22 exceeds 60.0% by mass, it may cause powdering, so it is preferably 60.0% by mass or less. It is also preferable that the total content of metal phosphate and silica is 70.0% by mass or more.
  • the remainder other than the metal phosphate and silica may include ceramic particles such as alumina and silicon nitride.
  • the metal phosphate aluminum phosphate is preferable from the viewpoint of heat resistance.
  • the thickness of the tensile coating layer 22 is not limited, but the average thickness of the insulating coating 2 (intermediate layer 21 + tensile coating layer 22) is preferably 2.0 to 20.0 ⁇ m when the average thickness of the intermediate layer 21 is in the above range. If the average thickness of the insulating coating 2 is less than 2.0 ⁇ m, sufficient coating tension cannot be obtained. Also, there is a large amount of phosphoric acid eluted. In this case, it may cause stickiness and reduced corrosion resistance, and may even cause the coating to peel off. Also, if the thickness of the insulating coating 2 exceeds 20.0 ⁇ m, the space factor may decrease and the magnetic properties may deteriorate, or cracks may occur, causing reduced adhesion and reduced corrosion resistance.
  • the mass proportion of the metal phosphate and the type of the metal phosphate can be determined in a cross section along the thickness direction in the same manner as in the intermediate layer 21.
  • the tensile coating layer 22 and the intermediate layer 21 can be distinguished by their different silica contents.
  • the thickness of the tensile coating layer 22 can be determined in the same manner as the intermediate layer 21.
  • the sum of the thickness of the tensile coating layer 22 and the thickness of the intermediate layer 21 is the thickness of the insulating coating 2.
  • the grain-oriented electrical steel sheet according to the present embodiment can be suitably manufactured by a manufacturing method that satisfies the manufacturing conditions described below.
  • the grain-oriented electrical steel sheet according to the present embodiment is not limited to a particular manufacturing method.
  • the grain-oriented electrical steel sheet having the above-mentioned configuration is considered to be the grain-oriented electrical steel sheet according to the present embodiment, regardless of its manufacturing conditions.
  • the grain-oriented electrical steel sheet according to this embodiment can be manufactured by a manufacturing method including the following steps.
  • IV a decarburization annealing step of performing decarburization annealing on the steel sheet after the cold rolling step;
  • the treatment liquid in the immersion step satisfies the following conditions.
  • metal ion concentration 1.0 to 10.0 g/L
  • Phosphate ion concentration 2.0 to 25.0 g/L
  • C a nitrate ion concentration of 2.0 to 40.0 g/L
  • D an iron ion concentration of 1.0 to 20.0 g/L
  • E the ratio of the phosphate ion concentration to the metal ion concentration is 1.5 to 5.0
  • the ratio of the nitrate ion concentration to the phosphate ion concentration is 0.5 to 10.0.
  • the method for producing the grain-oriented electrical steel sheet according to this embodiment further includes the steps of: (XII) a nitriding process for performing a nitriding process on the steel sheet between the decarburization annealing process and the finish annealing process; (XIII) a magnetic domain refining step for controlling magnetic domains of the steel sheet after the tensile coating layer forming step; may include either or both of the following:
  • the manufacturing process of the grain-oriented electrical steel sheet according to this embodiment is characterized by the steps (V) finish annealing step to (XI) tensile coating layer forming step (which may be collectively referred to as the insulating coating forming step), which are mainly related to the formation of the insulating coating, and publicly known conditions can be adopted for the other steps or conditions not described. These steps will be described below.
  • a steel billet such as a slab having a predetermined chemical composition is heated and then hot rolled to obtain a hot-rolled sheet.
  • the heating temperature of the steel billet is preferably within a range of 1100 to 1450°C.
  • the heating temperature is more preferably 1300 to 1400°C.
  • the chemical composition of the steel billet may be changed depending on the chemical composition of the grain-oriented electrical steel sheet that is ultimately desired, but an example of a chemical composition that may be used is, in mass %, C: 0.01-0.20%, Si: 2.50-4.00%, sol. Al: 0.01-0.040%, Mn: 0.01-0.50%, N: 0.020% or less, S: 0.005-0.040%, Cu: 0-0.50%, Sn: 0-0.50%, Se: 0-0.020%, Sb: 0-0.50%, and the balance being Fe and impurities.
  • Hot rolling conditions are not particularly limited and may be set appropriately based on the desired characteristics.
  • the thickness of the hot rolled sheet is preferably within the range of 2.0 mm to 3.0 mm, for example.
  • the hot-rolled sheet annealing process is a process of annealing the hot-rolled sheet manufactured through the hot rolling process. By carrying out such an annealing treatment, recrystallization occurs in the steel sheet structure, and it is possible to realize good magnetic properties, which is preferable.
  • the hot-rolled sheet produced through a hot rolling process may be annealed according to a known method.
  • the means for heating the hot-rolled sheet during annealing is not particularly limited, and any known heating method may be used.
  • the annealing conditions are not particularly limited.
  • the hot-rolled sheet may be annealed in a temperature range of 900 to 1200°C for 10 seconds to 5 minutes.
  • Cold rolling process In the cold rolling process, the hot rolled sheet after the hot rolled sheet annealing process is subjected to cold rolling to obtain a steel sheet (cold rolled sheet).
  • the cold rolling may be a single cold rolling (a series of cold rolling without annealing in between), or may be a multiple cold rolling with intermediate annealing between them, in which the cold rolling is interrupted and at least one or two or more intermediate annealings are performed before the final pass of the cold rolling process.
  • intermediate annealing When intermediate annealing is performed, it is preferable to hold the steel sheet at a temperature of 1000 to 1200° C. for 5 to 180 seconds.
  • the annealing atmosphere is not particularly limited. In consideration of the manufacturing cost, it is preferable to perform intermediate annealing three times or less. Furthermore, the surface of the hot-rolled sheet may be subjected to pickling before the cold rolling step.
  • the hot rolled sheet after the hot rolled sheet annealing step may be cold rolled to obtain a steel sheet according to a known method.
  • the final rolling reduction may be in the range of 80 to 95%. If the final rolling reduction is 80% or more, it is preferable because Goss nuclei having a high concentration of ⁇ 110 ⁇ 001> orientation in the rolling direction can be obtained. On the other hand, if the final rolling reduction exceeds 95%, it is not preferable because the secondary recrystallization is likely to become unstable in the subsequent finish annealing step.
  • the final rolling reduction is the cumulative rolling reduction of cold rolling, and in the case where intermediate annealing is performed, it is the cumulative rolling reduction of cold rolling after final intermediate annealing.
  • the obtained steel sheet is subjected to decarburization annealing.
  • the conditions of the decarburization annealing are not limited as long as the steel sheet is subjected to primary recrystallization and C, which adversely affects magnetic properties, can be removed from the steel sheet.
  • the oxidation degree (PH 2 O/PH 2 ) in the annealing atmosphere (furnace atmosphere) is set to 0.3 to 0.6
  • the annealing temperature is set to 800 to 900° C. and held for 10 to 600 seconds.
  • a nitriding treatment may be carried out between the decarburization annealing step and the finish annealing step described below.
  • the steel sheet after the decarburization annealing process is maintained at about 700 to 850°C in a nitriding atmosphere (an atmosphere containing a gas having nitriding ability such as hydrogen, nitrogen, and ammonia) to perform the nitriding process.
  • a nitriding atmosphere an atmosphere containing a gas having nitriding ability such as hydrogen, nitrogen, and ammonia
  • AlN is used as an inhibitor, it is preferable that the N content of the steel sheet after the nitriding process is 40 ppm or more by the nitriding process.
  • the N content of the steel sheet after the nitriding process exceeds 1000 ppm, excessive AlN is present in the steel sheet even after the completion of secondary recrystallization in the finish annealing. Such AlN causes iron loss deterioration. For this reason, it is preferable that the N content of the steel sheet after the nitriding process is 1000 ppm or less.
  • annealing separator containing 10 to 100 mass% of Al 2 O 3 is applied to the steel sheet after the decarburization annealing process or after the nitriding process (after the nitriding process), dried, and then final annealing is performed.
  • a forsterite-based coating is formed on the surface of a steel sheet (cold-rolled sheet) by applying an annealing separator mainly composed of MgO and then performing finish annealing.
  • an annealing separator containing Al 2 O 3 is used so that a forsterite-based coating is hardly formed.
  • the proportion of Al 2 O 3 may be 100% by mass, but in order to prevent Al 2 O 3 from seizing onto the steel sheet surface, in the manufacturing method of the grain-oriented electrical steel sheet according to the present embodiment, it is preferable that the annealing separator contains MgO. Although MgO may be 0%, in order to obtain the above effect, it is preferable that the proportion of MgO is 5% by mass or more. In the case where MgO is contained, the proportion of MgO is 90% by mass or less in order to ensure 10% by mass or more of Al 2 O 3. The proportion of MgO is preferably 50% by mass or less.
  • the annealing separator may further contain chloride.
  • the annealing separator contains chloride, the effect of making it more difficult for a forsterite-based coating to form is obtained.
  • the chloride content is not particularly limited and may be 0%, but when obtaining the above effect, 0.5 to 10 mass% is preferable.
  • chlorides that are effective include bismuth chloride, calcium chloride, cobalt chloride, iron chloride, and nickel chloride.
  • annealing separator removal process In the annealing separator removing step, excess annealing separator is removed from the steel sheet after the final annealing step.
  • the excess annealing separator can be removed by washing with water.
  • the steel sheet after the annealing separator removal process is pickled for 1 to 20 seconds with one inorganic acid selected from sulfuric acid, phosphoric acid, nitric acid, and chloric acid, at 0.1 to 10 mass %, and heated to 30 to 85° C.
  • one inorganic acid selected from sulfuric acid, phosphoric acid, nitric acid, and chloric acid, at 0.1 to 10 mass %, and heated to 30 to 85° C.
  • the treatment solution is adjusted to satisfy the following conditions (A) to (F).
  • the treatment solution contains a metal phosphate and nitric acid as an oxidizing agent.
  • the metal phosphate include zinc phosphate, manganese phosphate, zinc calcium phosphate, and iron manganese phosphate. From the viewpoint of controllability of the unevenness index, zinc phosphate is preferred.
  • the metal ion concentration and phosphate ion concentration in the treatment solution are 1.0 to 10.0 g/L and 2.0 to 25.0 g/L, respectively.
  • the metal ion concentration and phosphate ion concentration are 1.0 g/L or more and 2.0 g/L or more, respectively.
  • the metal ion concentration and the phosphate ion concentration are 10.0 g/L or less and 25.0 g/L or less, respectively.
  • nitric acid is added as an oxidizing agent to the treatment liquid according to the present embodiment.
  • nitric acid as an oxidizing agent, hydrogen gas generation can be prevented and a dense intermediate layer can be efficiently formed.
  • the nitrate ion concentration is preferably 40.0 g/L or less.
  • the acid ion concentration is preferably 2.0 g/L or more.
  • the ratio of the phosphate ion concentration to the metal ion concentration is set to 1.5 to 5.0. If the ratio of the phosphate ion concentration to the metal ion concentration is too large, etching may proceed, causing the steel sheet to become excessively uneven, resulting in poor space factor.
  • the ratio of the phosphate ion concentration to the metal ion concentration is set to 5.0 or less.
  • the ratio of the phosphate ion concentration to the metal ion concentration is set to 1.5 or more.
  • Ratio of nitrate ion concentration to phosphate ion concentration 0.5 to 10.0
  • the ratio of the nitrate ion concentration to the phosphate ion concentration is also adjusted. Specifically, the ratio of the nitrate ion concentration to the phosphate ion concentration (nitrate ion concentration/phosphate ion concentration) is set to 0.5 to 10.0. If the ratio of the nitrate ion concentration to the phosphate ion concentration is too large, the etching of the steel sheet may be excessive. Therefore, the ratio of the nitrate ion concentration to the phosphate ion concentration is preferably set to 10.0 or less.
  • the ratio of the nitrate ion concentration to the phosphate ion concentration is preferably set to 0.5 or more.
  • the temperature of the treatment liquid is preferably 20 to 85°C, and the immersion time is preferably 5 to 150 seconds. If the liquid temperature is below 20°C or the treatment time is less than 5 seconds, the intermediate layer may not be sufficiently formed, resulting in poor adhesion. On the other hand, if the liquid temperature is above 85°C or the treatment time is more than 150 seconds, there may be areas in the intermediate layer where the crystalline metal phosphate is partially and excessively precipitated, resulting in poor space factor.
  • the drying temperature is preferably 300°C or less. More preferably, it is 200°C or less.
  • the drying temperature is preferably 100°C or more.
  • a coating liquid containing metal phosphate and colloidal silica and having a concentration of 10 to 40 mass % is applied to the steel sheet after the drying process, dried, and then heated until the sheet temperature reaches 1000° C. By holding the temperature at 700 to 950° C. for 10 to 50 seconds, a tensile coating layer is formed on the surface of the intermediate layer.
  • the sheet temperature during holding is below 700°C, the tension will be low and the magnetic properties will be inferior. Therefore, it is preferable to keep the sheet temperature at 700°C or higher.
  • the sheet temperature exceeds 950°C, the rigidity of the steel sheet will decrease and it will become more susceptible to deformation. In this case, the steel sheet may become distorted due to transportation, etc., resulting in inferior magnetic properties. Therefore, it is preferable to keep the sheet temperature at 950°C or lower.
  • the retention time should be 10 seconds or more.
  • the retention time is more than 50 seconds, the adhesion of the tensile coating layer may be poor. Therefore, a retention time of 50 seconds or less is preferable.
  • the coating liquid (insulating coating solution) is adjusted so that it contains a total of 10 to 40 mass % of metal phosphate and colloidal silica in terms of solid content. If the total concentration of the metal phosphate and colloidal silica is less than 10% by mass, the applied treatment liquid may flow easily, resulting in uneven application. If the total concentration of the metal phosphate and colloidal silica is more than 40% by mass, the viscosity may be too high, resulting in uneven patterns or application.
  • metal phosphate for example, one or a mixture of two or more selected from aluminum phosphate, zinc phosphate, magnesium phosphate, nickel phosphate, copper phosphate, lithium phosphate, cobalt phosphate, etc. can be used. Among these, aluminum phosphate is preferred.
  • the coating liquid may contain additional elements such as vanadium, tungsten, molybdenum, zirconium, etc. When these elements are contained, they can be added to the coating liquid, for example, as an oxygen acid.
  • Colloidal silica can be of type S or type C.
  • Type S colloidal silica refers to an alkaline silica solution
  • type C refers to an alkaline to neutral silica solution in which the silica particle surface is aluminum-treated.
  • Type S colloidal silica is widely used and is relatively inexpensive, but care must be taken as it may aggregate and precipitate when mixed with an acidic metal phosphate solution.
  • Type C colloidal silica is stable even when mixed with a metal phosphate solution and there is no risk of precipitation, but it is relatively expensive as it requires many processing steps. It is preferable to use the appropriate type depending on the stability of the coating liquid to be prepared.
  • the method for producing a grain-oriented electrical steel sheet according to this embodiment may further include a magnetic domain refining step of subjecting the steel sheet after the tensile coating layer forming step to magnetic domain refining. By performing magnetic domain refining treatment, it is possible to further reduce the core loss of grain-oriented electrical steel sheet.
  • Methods of magnetic domain subdivision include a method of narrowing the width of 180° magnetic domains (subdividing 180° magnetic domains) by forming linear or dot-like grooves extending in a direction intersecting the rolling direction at predetermined intervals along the rolling direction, and a method of narrowing the width of 180° magnetic domains (subdividing 180° magnetic domains) by forming linear or dot-like stress distortion portions or grooves extending in a direction intersecting the rolling direction at predetermined intervals along the rolling direction.
  • the stress-strained portion laser beam irradiation, electron beam irradiation, etc. can be applied.
  • a mechanical groove forming method using gears, etc. a chemical groove forming method in which a groove is formed by electrolytic etching, and a thermal groove forming method using laser irradiation can be applied.
  • the insulating coating may be formed again to repair the damage.
  • the slab was heated to 1350° C. and then hot-rolled to form a hot-rolled sheet having a thickness of 2.2 mm.
  • This hot-rolled sheet was annealed under conditions of holding at 1100° C. for 10 seconds (hot-rolled sheet annealing). Thereafter, the hot-rolled sheet was subjected to cold rolling to obtain a cold-rolled sheet having a sheet thickness of 0.22 mm.
  • This cold rolled sheet was subjected to decarburization annealing under conditions of holding at 830° C. for 90 seconds.
  • an annealing separator containing 95% MgO and Al2O3 and 5% BiCl3 (bismuth chloride) was applied, dried, and then finish annealed at 1200 ° C for 20 hours. After the finish annealing, the steel sheet was washed with water to remove the excess annealing separator, but no forsterite-based film was formed on the surface of the steel sheet. This steel sheet was lightly pickled with 3 mass % sulfuric acid at 80° C. for 10 seconds.
  • an intermediate layer was formed using the treatment solution shown in Table 1.
  • Steel wool was used as the source of iron ions, and the treatment solution was adjusted to the concentration shown in Table 1.
  • the immersion conditions were as shown in Table 1.
  • the obtained intermediate layer was as shown in Table 1.
  • an insulating coating treatment solution containing metal phosphate and colloidal silica as main components as shown in Table 2 was applied, and then dried at 850° C. for 20 seconds to form a tensile coating layer on the surface of the steel sheet.
  • the "molar ratio of metal elements" in Table 2 indicates the ratio of the metal elements when two or more metal elements are present in the metal phosphate.
  • the thickness of the insulating coating (intermediate layer and tensile coating layer) was as shown in Table 2.
  • the tensile coating layer consisted essentially of metal phosphate and silica.
  • the obtained steel sheet (grain-oriented electrical steel sheet) was subjected to a magnetic domain refinement process by irradiating a laser beam under conditions of a UA (irradiation energy density) of 2.0 J and an irradiation interval of 5.0 mm pitch.
  • the iron loss W17/50 (iron loss at 50 Hz at 1.7 T) of the steel sheet after the magnetic domain refining process was measured by a single sheet magnetic property measurement method (Single Sheet Tester: SST) in accordance with JIS C2556 (2015). If the iron loss W17/50 was 0.68 W/kg or less, it was determined that good magnetic properties were ensured.
  • the space factor was measured as follows.
  • Space factor The space factor was measured according to a method in accordance with JIS C 2550-5 (2020). Thirty test pieces, each 30 mm wide and 320 mm long, were used. After measuring the total mass of the sample, the gap between the upper and lower backing plates sandwiching the laminate was measured and calculated under a pressure of 1 MPa. If the space factor was 96.0% or more, it was determined that a high space factor was ensured.
  • the coating tension was calculated by back-calculating from the state of curvature when one side of the insulating coating was peeled off. When the obtained coating tension was 4.0 MPa or more, it was determined that the coating had sufficient tension.
  • the corrosion resistance was evaluated by subjecting the sample to a 5% NaCl aqueous solution that was allowed to fall naturally onto the sample for 7 hours in a 35° C. atmosphere in accordance with the JIS salt spray test (JIS Z2371:2015). Thereafter, the area of rust was evaluated on a scale of 1 to 10.
  • the evaluation criteria were as follows: With regard to corrosion resistance, a rating of 5 or more was deemed to be excellent in corrosion resistance.
  • the resistance to elution was evaluated based on whether or not the elution of phosphoric acid from the sample could be inhibited.
  • the amount of elution was measured by boiling the sample in boiling pure water for 10 minutes, measuring the amount of phosphoric acid eluted in the pure water, and dividing the amount of phosphoric acid by the area of the insulating coating of the boiled grain-oriented electrical steel sheet.
  • the amount of phosphoric acid eluted in the pure water was calculated by cooling the pure water (solution) into which the phosphoric acid had been eluted, diluting the cooled solution with pure water, and measuring the phosphoric acid concentration of the sample by ICP-AES. If the amount of elution was less than 40 mg/ m2 , the elution resistance was deemed to be excellent.
  • the examples of the present invention are extremely excellent in various properties, including the coating adhesion, and the core loss and space factor are improved.
  • the comparative examples were inferior in one or more of the coating adhesion, magnetic properties, corrosion resistance, elution resistance, and space factor of the transformer (core).
  • the above aspect of the present invention provides a grain-oriented electrical steel sheet that has excellent adhesion and magnetic properties of the tensile coating and does not reduce the space factor of the transformer (core). Therefore, the grain-oriented electrical steel sheet obtained can be suitably applied to the iron core material of a transformer, and has high industrial applicability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electromagnetism (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)
  • Soft Magnetic Materials (AREA)
PCT/JP2024/014841 2023-04-12 2024-04-12 方向性電磁鋼板および絶縁被膜の形成方法 Ceased WO2024214818A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202480024429.6A CN120958172A (zh) 2023-04-12 2024-04-12 取向性电磁钢板和绝缘覆膜的形成方法
KR1020257034143A KR20250163937A (ko) 2023-04-12 2024-04-12 방향성 전자 강판 및 절연 피막의 형성 방법
JP2025514033A JPWO2024214818A1 (https=) 2023-04-12 2024-04-12
EP24788840.7A EP4696809A1 (en) 2023-04-12 2024-04-12 Grain-oriented electrical steel sheet and method for forming insulating coating film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023064826 2023-04-12
JP2023-064826 2023-04-12

Publications (1)

Publication Number Publication Date
WO2024214818A1 true WO2024214818A1 (ja) 2024-10-17

Family

ID=93059612

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/014841 Ceased WO2024214818A1 (ja) 2023-04-12 2024-04-12 方向性電磁鋼板および絶縁被膜の形成方法

Country Status (5)

Country Link
EP (1) EP4696809A1 (https=)
JP (1) JPWO2024214818A1 (https=)
KR (1) KR20250163937A (https=)
CN (1) CN120958172A (https=)
WO (1) WO2024214818A1 (https=)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4839338A (https=) 1971-09-27 1973-06-09
JPS4996920A (https=) 1973-01-22 1974-09-13
JPS60240108A (ja) * 1984-05-14 1985-11-29 Kawasaki Steel Corp 超低鉄損方向性けい素鋼板およびその製造方法
JPH05279747A (ja) * 1992-04-02 1993-10-26 Nippon Steel Corp 方向性電磁鋼板の絶縁皮膜形成方法
JPH06184762A (ja) 1992-08-25 1994-07-05 Nippon Steel Corp 一方向性珪素鋼板の絶縁皮膜形成方法
JPH11209891A (ja) 1997-10-14 1999-08-03 Nippon Steel Corp 電磁鋼板の絶縁皮膜形成方法
JP2005139481A (ja) 2003-11-04 2005-06-02 Nippon Steel Corp 張力付与性絶縁皮膜の皮膜密着性に優れる一方向性珪素鋼板の製造方法
JP2016145419A (ja) * 2015-01-30 2016-08-12 Ｊｆｅスチール株式会社 方向性電磁鋼板とその製造方法
WO2019013347A1 (ja) * 2017-07-13 2019-01-17 新日鐵住金株式会社 方向性電磁鋼板、及び方向性電磁鋼板の製造方法
WO2022215710A1 (ja) 2021-04-06 2022-10-13 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法
WO2022215709A1 (ja) * 2021-04-06 2022-10-13 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法
JP2023064826A (ja) 2021-10-27 2023-05-12 トヨタ自動車株式会社 複合溶射材料及びその製造方法、これを用いた電極

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4839338A (https=) 1971-09-27 1973-06-09
JPS4996920A (https=) 1973-01-22 1974-09-13
JPS60240108A (ja) * 1984-05-14 1985-11-29 Kawasaki Steel Corp 超低鉄損方向性けい素鋼板およびその製造方法
JPH05279747A (ja) * 1992-04-02 1993-10-26 Nippon Steel Corp 方向性電磁鋼板の絶縁皮膜形成方法
JPH06184762A (ja) 1992-08-25 1994-07-05 Nippon Steel Corp 一方向性珪素鋼板の絶縁皮膜形成方法
JPH11209891A (ja) 1997-10-14 1999-08-03 Nippon Steel Corp 電磁鋼板の絶縁皮膜形成方法
JP2005139481A (ja) 2003-11-04 2005-06-02 Nippon Steel Corp 張力付与性絶縁皮膜の皮膜密着性に優れる一方向性珪素鋼板の製造方法
JP2016145419A (ja) * 2015-01-30 2016-08-12 Ｊｆｅスチール株式会社 方向性電磁鋼板とその製造方法
WO2019013347A1 (ja) * 2017-07-13 2019-01-17 新日鐵住金株式会社 方向性電磁鋼板、及び方向性電磁鋼板の製造方法
WO2022215710A1 (ja) 2021-04-06 2022-10-13 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法
WO2022215709A1 (ja) * 2021-04-06 2022-10-13 日本製鉄株式会社 方向性電磁鋼板及び絶縁被膜の形成方法
JP2023064826A (ja) 2021-10-27 2023-05-12 トヨタ自動車株式会社 複合溶射材料及びその製造方法、これを用いた電極

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4696809A1

Also Published As

Publication number Publication date
JPWO2024214818A1 (https=) 2024-10-17
KR20250163937A (ko) 2025-11-21
CN120958172A (zh) 2025-11-14
EP4696809A1 (en) 2026-02-18

Similar Documents

Publication Publication Date Title
JP7678366B2 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
JP7727214B2 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
WO2019013351A1 (ja) 方向性電磁鋼板及びその製造方法
JP7727215B2 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
JP7553869B2 (ja) 方向性電磁鋼板
JP7783550B2 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
JP7787460B2 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
JP7817624B2 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
WO2024214818A1 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
JP7748016B2 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
JP7795149B2 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
JP7730076B2 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
JP7748015B2 (ja) 方向性電磁鋼板および絶縁被膜の形成方法
WO2025170057A1 (ja) 方向性電磁鋼板及びその製造方法
RU2842744C2 (ru) Лист электротехнической стали с ориентированной зеренной структурой и способ формирования изоляционного покрытия
WO2025170056A1 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
WO2024171608A1 (ja) 方向性電磁鋼板、並びに、方向性電磁鋼板の中間層および絶縁被膜の形成方法
WO2025170059A1 (ja) 方向性電磁鋼板及び絶縁被膜の形成方法
WO2024210203A1 (ja) 方向性電磁鋼板及び絶縁被膜形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24788840

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2025514033

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202517095059

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 1020257034143

Country of ref document: KR

Free format text: ST27 STATUS EVENT CODE: A-0-1-A10-A15-NAP-PA0105 (AS PROVIDED BY THE NATIONAL OFFICE)

WWE Wipo information: entry into national phase

Ref document number: KR1020257034143

Country of ref document: KR

Ref document number: 1020257034143

Country of ref document: KR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112025021738

Country of ref document: BR

WWE Wipo information: entry into national phase

Ref document number: 2024788840

Country of ref document: EP

Ref document number: 2025128366

Country of ref document: RU

NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 202517095059

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

WWP Wipo information: published in national office

Ref document number: 2025128366

Country of ref document: RU

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

ENP Entry into the national phase

Ref document number: 2024788840

Country of ref document: EP

Effective date: 20251112

WWP Wipo information: published in national office

Ref document number: 2024788840

Country of ref document: EP