WO2021261517A1 - 方向性電磁鋼板の製造方法 - Google Patents
方向性電磁鋼板の製造方法 Download PDFInfo
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- WO2021261517A1 WO2021261517A1 PCT/JP2021/023783 JP2021023783W WO2021261517A1 WO 2021261517 A1 WO2021261517 A1 WO 2021261517A1 JP 2021023783 W JP2021023783 W JP 2021023783W WO 2021261517 A1 WO2021261517 A1 WO 2021261517A1
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- 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
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1255—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest with diffusion of elements, e.g. decarburising, nitriding
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1261—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest following hot rolling
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1272—Final recrystallisation annealing
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
- C21D8/1277—Modifying the physical properties 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
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- 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
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- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- 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
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
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- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/05—Grain orientation
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- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Definitions
- the present invention relates to a method for manufacturing a grain-oriented electrical steel sheet.
- the grain-oriented electrical steel sheet is a steel sheet containing Si in an amount of about 2% by mass to 5% by mass, and the orientation of the crystal grains of the steel sheet is highly integrated in the ⁇ 110 ⁇ ⁇ 001> orientation called the Goss orientation.
- the grain-oriented electrical steel sheet has excellent magnetic characteristics and is used, for example, as an iron core material for a static induction device such as a transformer.
- the crystal orientation is controlled by utilizing a catastrophic grain growth phenomenon called secondary recrystallization.
- secondary recrystallization it is important to improve the heat resistance of fine precipitates in steel called inhibitors.
- the inhibitor is completely solid-dissolved when the steel piece is heated before hot rolling, and then finely precipitated in the hot rolling and the subsequent annealing step.
- Patent Documents 3 and 4 disclose a technique for manufacturing a grain-oriented electrical steel sheet having excellent film characteristics by controlling the conditions of hot-rolled sheet annealing and the pickling treatment conditions.
- Patent Document 5 discloses a technique for producing grain-oriented electrical steel having excellent film characteristics by controlling the pickling treatment conditions, the additive conditions of the annealing separator, and the finish annealing conditions.
- Patent Document 6 discloses a technique for producing a grain-oriented electrical steel sheet having excellent magnetic properties by controlling carbides by heat treatment before cold rolling.
- Patent Document 7 discloses a technique for producing grain-oriented electrical steel having excellent magnetic properties by controlling the temperature rise process of primary recrystallization annealing and introducing a slight strain during the temperature rise process. ing.
- Patent Document 8 discloses a technique for manufacturing a grain-oriented electrical steel sheet having low iron loss over the entire length of the coil by controlling the heat pattern in the heating process of primary recrystallization annealing.
- Patent Document 9 describes a technique for reducing the iron loss value of grain-oriented electrical steel sheets by strictly controlling the average grain size of crystal grains after secondary recrystallization and the deviation angle from the ideal orientation. Is disclosed.
- the grain-oriented electrical steel sheet which is the main member, is also required to have reliability that contributes to the stable operation of the transformer.
- the uniform appearance of grain-oriented electrical steel sheets without color unevenness is an important factor in gaining the trust of consumers.
- Patent Documents 3 to 5 disclose a technique for improving the film adhesion by causing a difference in the concentration of Mn and Cu between the surface of the steel sheet and the center of the plate thickness.
- the technique for concentrating a specific component on the surface of a steel sheet is intended only for improving the coating properties, and a technique for stably obtaining good magnetic properties has not been studied.
- Patent Document 6 discloses that the heat treatment before cold rolling promotes the change from cementite to graphite and improves the texture obtained by the subsequent primary recrystallization.
- the heating process and pickling of the primary recrystallization annealing follow the conventional method, and no new study has been made.
- Patent Document 7 in the heating process of primary recrystallization annealing, the temperature is rapidly raised to a temperature of 700 ° C. or higher at 100 ° C./s or higher, and the nominal strain is 0 during this rapid heating. It has been confirmed that the introduction of a fine strain of 1% or more has a great influence on the magnetic properties of grain-oriented electrical steel sheets. Further, in Patent Document 8, in the process of raising the temperature of the primary recrystallization annealing, the temperature is rapidly raised at 100 ° C./s or higher between 500 ° C. and 600 ° C., which has a great influence on the magnetic properties of the grain-oriented electrical steel sheet. It has been confirmed that it will be given. Patent Document 9 discloses that the temperature rise to 850 ° C. is set to 300 ° C./s or 450 ° C./s in the temperature rise process of primary recrystallization annealing.
- Patent Documents 7 to 9 it has not been investigated in detail how the magnetic properties of the grain-oriented electrical steel sheet are affected when the inhibitor is changed in the plate thickness direction of the steel sheet. ..
- the present invention has been made in view of the above problems and the like, and an object of the present invention is to realize a high magnetic flux density and to manufacture a grain-oriented electrical steel sheet having excellent magnetic characteristics. , To provide a new and improved method for manufacturing grain-oriented electrical steel sheets.
- C 0.01% or more and 0.10% or less
- Si 2.5% or more and 4.5% or less
- Mn 0.01% or more and 0.50% or less
- S, Se and Te Total of 1 type or 2 types or more 0.001% or more and 0.050% or less
- acid-soluble Al more than 0% and 0.05% or less
- N more than 0% and 0.015% or less
- the balance is Fe
- a step of obtaining a cold-rolled steel sheet by cold-rolling the hot-rolled steel sheet or the hot-rolled annealed sheet A step of obtaining a primary recrystallization annealed sheet by subjecting the cold-rolled steel sheet to primary recrystallization annealing, and A process of applying an annealing separator containing MgO to the surface of the primary recrystallization annealed plate and then performing finish annealing to obtain a finished annealed plate.
- At least one of the hot-rolled steel sheet, the hot-rolled annealed sheet, the cold-rolled steel sheet, and the primary recrystallized annealed sheet is subjected to a shot blast treatment and a treatment in contact with a solution.
- the average particle size of the projection material is 0.1 mm or more and 5.0 mm or less, and the projection speed is 10 m / s or more and 150 m / s or less.
- the solution contains one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni, and the total concentration of each element is 0.00001% or more and 1.0000% or less.
- the pH is ⁇ 1.5 or more and less than 7, the liquid temperature is 15 ° C. or more and 100 ° C. or less, and the time for the steel sheet to be immersed in the solution is 5 seconds or more and 200 seconds or less.
- a method for manufacturing a sex electromagnetic steel sheet is provided.
- a leveler processing may be performed in place of or in addition to the shot blasting described above.
- the heat-rolled steel sheet is bent twice or more, the bending angle is 10 degrees or more and 90 degrees or less, and the bending radius is 10 mm or more and 200 mm or less. Manufacturing method, is provided.
- a method for manufacturing a grain-oriented electrical steel sheet characterized in that the average temperature rise rate in the temperature range of 550 ° C to 700 ° C is 100 ° C / s or more and 3000 ° C / s or less in the rapid temperature rise of the primary recrystallization annealing. , Is provided.
- the slab replaces a part of the Fe with Cu: 1.0% or less, Sn: 1.0% or less, Ni: 1.0% or less, Cr: 1.0% or less, Sb: 1.0.
- a method for producing a directional electromagnetic steel plate which comprises one or more selected from the group consisting of% or less and Bi: 1.0% or less.
- the primary recrystallization annealing includes a step of raising the temperature, an intermediate treatment between the temperature rise and decarburization annealing, and a step of decarburization annealing.
- the intermediate treatment the dew point temperature of the atmosphere is ⁇ 40 ° C. or higher and 0 ° C. or lower
- the residence time of the steel plate temperature is 700 ° C. or higher and 950 ° C. or lower and the residence time is 1 second or longer and 20 seconds or lower.
- the decarburization annealing a method for manufacturing a grain-oriented electrical steel sheet, characterized in that the oxygen partial pressure ratio (PH2O / PH2) of the atmosphere is 0.35 or more and 0.60 or less, is provided.
- a solution containing one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni (these may be referred to as "Cu and the like” in the present specification).
- the electromagnetic steel plate are brought into contact with each other.
- the electrical steel sheet contains MnS, MnSe, MnTe (these may be referred to as “MnS and the like” in the present specification) as precipitates, and the precipitates such as MnS act as inhibitors.
- the heat resistance of the precipitate is improved by utilizing the phenomenon that when MnS or the like comes into contact with a solution containing Cu or the like, a part of Mn in MnS or the like, particularly Mn on the surface layer of MnS or the like is replaced with Cu or the like.
- the inhibitor strength of the directional electromagnetic steel plate can be improved.
- the magnetic flux density can be further increased by combining the technique of increasing the Goss directional particles in the vicinity of the surface layer by performing a rapid heat treatment in the heating process of the primary recrystallization annealing. ..
- the magnetic flux density can be further increased by combining a technique of adding an additive element to the slab to stabilize the secondary crystal.
- the present inventors have stated that the phenomenon in which Mn on the surface layer such as MnS is replaced with Cu or the like may cause color unevenness in the final product, but primary recrystallization annealing (rapid heat treatment, intermediate treatment and desorption). It was found that this can be solved by controlling and improving the atmosphere and temperature conditions in the intermediate treatment of charcoal annealing and the atmospheric conditions in decarburization annealing. According to another aspect of the present invention based on this finding, the color unevenness can be suppressed.
- the notation "A to B" for the numerical values A and B means “A or more and B or less”.
- the unit shall be applied to the numerical value A as well.
- the present inventors replace a part of Mn in MnS or the like, particularly Mn on the surface layer of MnS or the like with Cu or the like. It has been found that the inhibitor strength can be improved and the magnetic properties can be improved by improving the heat resistance of MnS or the like by utilizing this phenomenon. In addition, it has been found that the magnetic properties can be further improved by controlling the inhibitor in the plate thickness direction of the steel sheet by devising the pretreatment of the shot blast treatment or the leveler treatment when the solution is brought into contact with the steel sheet.
- the magnetic properties can be further improved by increasing the number of Goss azimuth particles in the vicinity of the surface layer by performing a rapid heat treatment in the heating process of the primary recrystallization annealing. It was also found that the magnetic properties can be further improved by adding an additive element to the slab to stabilize the secondary crystal. Further, the phenomenon that Mn on the surface layer such as MnS is replaced with Cu or the like may cause color unevenness in the final product, but is an intermediate treatment for primary recrystallization annealing (rapid heat treatment, intermediate treatment and decarburization annealing). It was found that this can be solved by controlling and improving the atmosphere and temperature conditions in the above and the atmosphere conditions in decarburization annealing.
- One embodiment of the present invention is a method for manufacturing a grain-oriented electrical steel sheet having the following configuration.
- C 0.01% or more and 0.10% or less
- Si 2.5% or more and 4.5% or less
- Mn 0.01% or more and 0.50% or less
- S, Se and Te 1 The total of seeds or two or more species: 0.001% or more and 0.050% or less, acid-soluble Al: more than 0% or more and 0.05% or less, N: more than 0% and 0.015% or less, and the balance is Fe.
- a step of obtaining a cold-rolled steel sheet by cold-rolling the hot-rolled steel sheet or the hot-rolled annealed sheet A step of obtaining a primary recrystallization annealed sheet by subjecting the cold-rolled steel sheet to primary recrystallization annealing, and A process of applying an annealing separator containing MgO to the surface of the primary recrystallization annealed plate and then performing finish annealing to obtain a finished annealed plate.
- At least one of the hot-rolled steel sheet, the hot-rolled annealed sheet, the cold-rolled steel sheet, and the primary recrystallized annealed sheet is subjected to a shot blast treatment and a treatment in contact with a solution.
- the average particle size of the projection material is 0.1 mm or more and 5.0 mm or less, and the projection speed is 10 m / s or more and 150 m / s or less.
- the solution contains one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni, and the total concentration of each element is 0.00001% or more and 1.0000% or less.
- the pH is ⁇ 1.5 or more and less than 7, the liquid temperature is 15 ° C. or higher and 100 ° C. or lower, and the time for the steel sheet to be immersed in the solution is 5 seconds or longer and 200 seconds or shorter.
- a leveler processing may be performed instead of or in addition to the shot blasting.
- the steel sheet is bent twice or more, the bending angle is 10 degrees or more and 90 degrees or less, and the bending radius is 10 mm or more and 200 mm or less.
- the temperature rising process of the primary recrystallization annealing may be a rapid temperature rise, and in the rapid temperature rise, the average temperature rise rate in the temperature range of 550 ° C to 700 ° C is 100 ° C / s or more and 3000 ° C / s or less. be.
- the primary recrystallization annealing may include a step of raising the temperature, an intermediate treatment between the temperature rise and the decarburization annealing, and a step of decarburization annealing.
- the intermediate treatment the dew point temperature of the atmosphere is ⁇ 40 ° C. or higher and 0 ° C. or lower, and the residence time of the steel plate temperature is 700 ° C. or higher and 950 ° C. or lower and the residence time is 1 second or longer and 20 seconds or lower.
- the oxygen partial pressure ratio ( PH2O / PH2 ) of the atmosphere is 0.35 or more and 0.60 or less.
- the component composition of the slab used for the grain-oriented electrical steel sheet according to the present embodiment will be described.
- the notation “%” means “mass%”.
- the rest of the slab other than the elements described below is Fe and impurities.
- the impurity refers to a component contained in the raw material or a component mixed in the manufacturing process and not intentionally contained in the steel sheet.
- the chemical composition of the slab which is the material of the grain-oriented electrical steel sheet, basically conforms to the composition of the grain-oriented electrical steel sheet.
- the slab as the raw material and the grain-oriented electrical steel sheets as the final product The chemical composition of is different.
- the slab composition can be appropriately adjusted in consideration of the effects of decarburization annealing and purification annealing in the manufacturing process so that the characteristics of the grain-oriented electrical steel sheet become desired.
- the C (carbon) content is 0.01% or more and 0.10% or less.
- C has various roles, but when the C content is less than 0.01%, the crystal grain size becomes excessively large when the slab is heated, resulting in iron loss of the final grain-oriented electrical steel sheet. It is not preferable because it increases the value.
- the C content is more than 0.10%, the decarburization time becomes long and the manufacturing cost increases during decarburization after cold rolling, which is not preferable. Further, when the C content is more than 0.10%, decarburization tends to be incomplete, which may cause magnetic aging in the final grain-oriented electrical steel sheet, which is not preferable. Therefore, the content of C is 0.01% or more and 0.10% or less, preferably 0.05% or more and 0.09% or less.
- the content of Si (silicon) is 2.5% or more and 4.5% or less.
- Si reduces the eddy current loss, which is one of the causes of iron loss, by increasing the electric resistance of the steel sheet.
- the Si content is less than 2.5%, it becomes difficult to sufficiently suppress the eddy current loss of the final grain-oriented electrical steel sheet, which is not preferable.
- the Si content is more than 4.5%, the workability of the grain-oriented electrical steel sheet is deteriorated, which is not preferable. Therefore, the Si content is 2.5% or more and 4.5% or less, preferably 2.7% or more and 4.0% or less.
- the content of Mn (manganese) is 0.01% or more and 0.50% or less.
- Mn forms MnS, MnSe, MnTe and the like, which are inhibitors that influence secondary recrystallization.
- the Mn content is less than 0.01%, the absolute amounts of MnS, MnSe and MnTe that cause secondary recrystallization are insufficient, which is not preferable.
- the Mn content is more than 0.50%, it is not preferable because it becomes difficult to dissolve Mn during slab heating.
- the Mn content is 0.01% or more and 0.50% or less, preferably 0.01% or more and 0.30% or less. More preferably, it is 0.03% or more and 0.15% or less.
- the total content of one or more of S (sulfur), Se (selenium) and Te is 0.001% or more and 0.050% or less in total.
- S, Se and Te form an inhibitor together with Mn described above.
- Two or more kinds of S, Se and Te may be contained in the slab, but at least one of them may be contained in the slab. If the total content of S, Se and Te is out of the above range, a sufficient inhibitory effect cannot be obtained, which is not preferable. Therefore, the total content of S, Se and Te is 0.001% or more and 0.050% or less, preferably 0.002% or more and 0.040% or less.
- the content of acid-soluble Al is more than 0% and 0.05% or less.
- the acid-soluble Al constitutes an inhibitor necessary for producing a grain-oriented electrical steel sheet having a high magnetic flux density.
- the content of the acid-soluble Al is 0, AlN does not exist, the inhibitor strength may be insufficient, and good magnetic properties may not be obtained, which is not preferable.
- the content of the acid-soluble Al is more than 0.05%, AlN precipitated as an inhibitor is coarsened and the inhibitor strength is lowered, which is not preferable. Therefore, the content of acid-soluble Al is more than 0% and 0.05% or less, preferably more than 0% and 0.04% or less.
- the content of N is more than 0% and 0.015% or less. N forms the inhibitor AlN together with the acid-soluble Al described above. If the content of N is out of the above range, a sufficient inhibitory effect cannot be obtained, which is not preferable. Therefore, the content of N is more than 0% and 0.015% or less, preferably more than 0% and 0.012% or less.
- P phosphorus
- P may be contained in an amount of more than 0% and 1.0% or less.
- P has the effect of increasing the strength without lowering the magnetic flux density.
- the upper limit of the amount of P is 1.0%. It is preferably 0.150% or less, more preferably 0.120% or less.
- the lower limit of the amount of P is not particularly limited, but it is 0.001% or more in consideration of the manufacturing cost.
- the slab used for manufacturing the grain-oriented electrical steel sheet according to the present embodiment contains Cu, Sn, Ni, Cr, Sb, or Bi as an element for stabilizing secondary recrystallization in addition to the above-mentioned elements. Any one or two or more may be contained.
- the slab contains the above elements, the magnetic flux density of the manufactured grain-oriented electrical steel sheet can be further improved.
- a slab is formed by casting molten steel adjusted to the composition of the composition described above.
- the method of casting the slab is not particularly limited. Further, in research and development, even if a steel ingot is formed in a vacuum melting furnace or the like, the same effect as when a slab is formed can be confirmed for the above components.
- the slab heating temperature is not particularly limited.
- the upper limit of the heating temperature of the slab at this time is not particularly determined, but is preferably 1450 ° C. from the viewpoint of equipment protection.
- the heating temperature of the slab may be 1280 ° C. or higher and 1450 ° C. or lower.
- the slab heating temperature may be set to less than 1280 ° C.
- the steel sheet may be nitrided in any of the hot rolling step or the hot rolling sheet annealing step to the finish annealing step.
- the thickness of the hot-rolled steel sheet after processing may be, for example, 1.8 mm or more and 3.5 mm or less. If the thickness of the hot-rolled steel sheet is less than 1.8 mm, the shape of the steel sheet after hot rolling may be inferior, which is not preferable. When the thickness of the hot-rolled steel sheet exceeds 3.5 mm, the rolling load in the cold rolling process becomes large, which is not preferable.
- a hot-rolled sheet may be annealed to obtain a hot-rolled sheet. When hot-rolled sheet is annealed, the shape of the steel sheet becomes better, so that the possibility of the steel sheet breaking in the cold rolling in the subsequent process can be reduced.
- the obtained hot-rolled steel sheet or hot-rolled annealed sheet is processed into a cold-rolled steel sheet by being rolled by one cold rolling or a plurality of cold rollings sandwiching intermediate annealing. ..
- intermediate annealing and / or a plurality of cold rollings with pickling sandwiched between them it is possible to omit the hot-rolled sheet annealing in the previous stage.
- pickling treatment it is preferable to perform a pickling treatment before each cold rolling step. Further, both hot-rolled sheet annealing and intermediate annealing may be performed.
- the steel sheet may be heat-treated at about 300 ° C. or lower between cold rolling passes, between rolling roll stands, or during rolling. In such a case, the magnetic properties of the final grain-oriented electrical steel sheet can be improved.
- the hot-rolled steel sheet may be rolled by cold rolling three or more times, but since the cold rolling a large number of times increases the manufacturing cost, the hot-rolled steel sheet is cold-rolled once or twice. It is preferably rolled by rolling.
- the cold rolling is performed by reverse rolling such as a Zendimia mill, the number of passes in each cold rolling is not particularly limited, but from the viewpoint of manufacturing cost, 9 times or less is preferable.
- Step of applying primary recrystallization annealing Next, the cold-rolled steel sheet is heated and then decarburized and annealed. These processes are also referred to as primary recrystallization annealing and are preferably carried out continuously. By rapidly increasing the temperature of the primary recrystallization annealing, it is possible to increase the Goss orientation grains before the secondary recrystallization in the cold-rolled steel sheet, resulting in a more ideal Goss orientation in the secondary recrystallization process. It is expected that the near-oriented grains will be recrystallized secondarily.
- the average heating rate between 550 ° C and 700 ° C may be rapidly set to 100 ° C / s or more and 3000 ° C / s or less.
- the temperature range for rapid temperature rise is 550 ° C to 700 ° C.
- the start temperature of the rapid temperature rise exceeds 550 ° C.
- the recovery of dislocations progresses greatly in the steel sheet, and the primary recrystallization of the orientation grains other than the Goss orientation grains starts, so that the effect of increasing the Goss orientation grains is reduced. Therefore, it is not preferable.
- the end temperature of the rapid temperature rise is less than 700 ° C.
- the primary recrystallization of other orientation grains is completed before the primary recrystallization of the Goss orientation grains is completed, so that the effect of increasing the Goss orientation grains is reduced. Not preferred.
- the Goss directional grains before the secondary recrystallization can be further increased, and the magnetic flux of the final directional electromagnetic steel plate can be further increased. It is more preferable because the density can be further improved, and when the average heating rate between 550 ° C and 700 ° C is 700 ° C / s or more, the magnetic flux density of the directional electromagnetic steel plate can be further improved. Extremely preferable. If the average heating rate between 550 ° C and 700 ° C is less than 100 ° C / s, sufficient Goss directional grains cannot be obtained in the secondary recrystallization to improve the magnetic properties, which is not preferable.
- the upper limit of the average temperature rise rate between 550 ° C and 700 ° C is not particularly limited, but may be, for example, 3000 ° C / s from the viewpoint of equipment and manufacturing cost.
- the heat pattern and the ultimate temperature other than the temperature rise start temperature of the primary recrystallization annealing and the rapid temperature rise of 550 ° C to 700 ° C are not particularly limited.
- Such rapid temperature rise can be carried out, for example, by using an energization heating method or an induction heating method.
- the temperature raising process may be carried out by a plurality of devices.
- recovery of the steel sheet that is, holding or slowly cooling at a temperature lower than 550 ° C., which causes a decrease in the dislocation density in the steel, can also improve the temperature soaking property of the steel sheet before the temperature rise. It doesn't matter.
- a heating process including a temperature increase from 550 ° C to 700 ° C may also be performed by one or more devices.
- the point at which the temperature rise is started is the transition from the state where the temperature of the steel sheet is lowered to the state where the temperature of the steel sheet is raised on the low temperature side of 550 ° C. or lower (that is, the point where the temperature change takes a minimum value). Is. Further, the point where the temperature rise is completed is the point where the temperature of the steel sheet changes from the state where the temperature of the steel sheet rises to the state where the temperature of the steel sheet decreases on the high temperature side of 700 ° C. or higher (that is, the point where the temperature change reaches a maximum value). ).
- the temperature of the steel sheet may continue to rise on the higher temperature side than the temperature raising process including 700 ° C.
- the rapid temperature rise end point may be 700 ° C. or higher, and the rate of change in the temperature rise rate may be the minimum with a negative value.
- the method for discriminating the temperature rise start point and the rapid temperature rise end point is not particularly limited, but it can be discriminated by measuring the steel plate temperature using, for example, a radiation thermometer or the like.
- the method for measuring the temperature of the steel sheet is not particularly limited. Further, even if the temperature rise end temperature of the primary recrystallization becomes lower or higher than the subsequent decarburization annealing temperature, the effect of the present invention is not impaired. If the temperature rise end temperature of the primary recrystallization is lower than the decarburization annealing temperature, heating may be performed in the decarburization annealing step.
- the steel sheet temperature may be cooled by performing heat treatment or gas cooling treatment. Further, after cooling to a temperature lower than the decarburization annealing temperature, reheating may be performed in the decarburization annealing step.
- the temperature on the entrance side and the temperature on the exit side of the steel sheet to the temperature riser in the temperature rise process may be set as a temperature rise start point and a rapid temperature rise end point.
- an intermediate treatment step is provided between the temperature raising step and the decarburization annealing step in the primary recrystallization annealing, and the dew point temperature of the atmosphere in the intermediate treatment step is ⁇ 40 ° C. or higher and 0 ° C. or lower.
- the residence time of the steel plate temperature of 700 ° C. or higher and 950 ° C. or lower may be 1 second or longer and 20 seconds or lower.
- the inhibitor can be controlled in the plate thickness direction of the steel sheet and the magnetic characteristics can be improved.
- the ingenuity of this solution contact treatment may cause a new demerit of color unevenness in the appearance of the steel sheet.
- the color unevenness in the appearance of the steel sheet is caused by the oxide film formation state after decarburization annealing, and more specifically, when the internal oxidation occurs non-uniformly, the color unevenness occurs in the appearance of the steel sheet.
- the present inventors have found that the atmosphere and temperature conditions can be controlled to suppress the occurrence of color unevenness before decarburization annealing, that is, in the intermediate treatment.
- the oxide film formation becomes non-uniform in the subsequent decarburization annealing, and the appearance of the directional electromagnetic steel sheet obtained as the final product becomes uneven, which is not preferable. ..
- the residence time of the steel sheet temperature of 700 ° C. or higher and 950 ° C.
- the upper limit of the residence time of the steel sheet temperature of 700 ° C. or higher and 950 ° C. or lower in the intermediate treatment is not particularly limited, but if it is more than 20 seconds, the equipment becomes long, which is not preferable.
- the mechanism by which the intermediate treatment affects the oxide film formation in the subsequent decarburization annealing is not necessarily clear, but is presumed as follows.
- a solution containing one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni (Cu, etc.) is brought into contact with the steel sheet (solution contact treatment)
- MnS on the surface layer side of the steel sheet is performed.
- MnSe or part of MnTe, Mn replaces these elements.
- Cu, Hg, Ag, Pb, Cd, Co, Zn or Ni are not uniformly distributed on the surface of the steel sheet and are localized in the place where MnS or the like is present.
- the dew point temperature in the intermediate treatment is less than -40 ° C, the amount of oxide film formed in the intermediate treatment is insufficient, especially in the places where Cu, Hg, Ag, Pb, Cd, Co, Zn or Ni are localized. , Not desirable.
- the dew point temperature in the intermediate treatment exceeds 0 ° C., an external oxidation type silica film is formed in the intermediate treatment, and the progress of internal oxidation is suppressed in the subsequent decarburization annealing, and the oxide film becomes thin. , Cu, Hg, Ag, Pb, Cd, Co, Zn or Ni are localized, and it is presumed that the insufficient amount of oxidation becomes apparent and color unevenness remains until the final product.
- the residence time of the steel sheet temperature of 700 ° C. or higher and 950 ° C. or lower in the intermediate treatment is less than 1 second, the amount of the oxide film formed in the intermediate treatment is insufficient, which is not preferable. If the residence time is more than 20 seconds, the equipment becomes long, which is not preferable.
- the decarburization annealing may be carried out at a temperature of 900 ° C. or lower in a moist atmosphere containing hydrogen and nitrogen from the viewpoint of decarburization property.
- the ratio P H2O / P H2 of the hydrogen partial pressure P H2 may be 0.35 to 0.60.
- the oxygen partial pressure ratio in the decarburized annealing atmosphere is less than 0.35, the oxide film becomes thin and the insufficient amount of oxidation becomes apparent at the location where Cu, Hg, Ag, Pb, Cd, Co, Zn or Ni are localized. It is not preferable because the color unevenness remains until the final product.
- the oxygen partial pressure ratio in the decarburized annealing atmosphere is more than 0.60, the magnetic characteristics are deteriorated, which is not preferable. Therefore, the oxygen partial pressure ratio in the decarburized annealing atmosphere is 0.35 or more and 0.60 or less.
- the cold-rolled steel sheet may be subjected to reduction annealing following decarburization annealing for the purpose of improving magnetic properties and coating properties.
- the cold-rolled steel sheet after the primary recrystallization annealing is subjected to finish annealing.
- an annealing separator containing MgO as a main component may be applied before finish annealing for the purpose of preventing seizure between steel sheets, forming a primary film, and controlling secondary recrystallization behavior.
- the annealing separator is generally applied and dried on the surface of a steel sheet in the state of a water slurry, but an electrostatic coating method or the like may be used.
- finish annealing is performed for the purpose of primary film formation and secondary recrystallization.
- Finish annealing may be performed by heat-treating the coiled steel sheet using, for example, a batch type heating furnace or the like.
- a purification treatment may be performed in which the coiled steel sheet is heated to a temperature of about 1200 ° C. and then held.
- the temperature of finish annealing is raised from about room temperature, and the rate of temperature rise of finish annealing varies, but the present invention is not particularly limited, and general finish annealing conditions can be used. Is. For example, it may be 5 ° C./h to 100 ° C./h from the viewpoint of productivity and general equipment restrictions. Further, other known heat patterns may be used. The heat pattern is not particularly limited even in the cooling process.
- the atmospheric gas composition in the finish annealing is not particularly limited.
- a mixed gas of nitrogen and hydrogen may be used. It may be a dry atmosphere or a moist atmosphere.
- the purified annealing may be dry hydrogen gas.
- Step of flattening and annealing Subsequently, after finish annealing, an insulating film containing, for example, aluminum phosphate or colloidal silica as a main component is applied to the surface of the steel sheet for the purpose of imparting insulation and tension to the steel sheet. After that, flattening annealing is performed for the purpose of baking the insulating film and flattening the steel sheet shape by finish annealing.
- the components of the insulating coating are not particularly limited as long as the steel sheet is provided with insulating properties and tension. Needless to say, in the present embodiment, the magnetic domain control process may be applied to the grain-oriented electrical steel sheet depending on the purpose of the consumer.
- Step of shot blasting and / or leveling the steel sheet and bringing it into contact with the solution at least one of a hot-rolled steel sheet, a hot-rolled annealed sheet, a cold-rolled steel sheet, and a primary recrystallization annealed sheet is shot-blasted and / or leveled and then immersed in a solution.
- the treatment of contact with the solution (hereinafter, also referred to as “solution contact treatment”) is performed at least once after hot rolling and before finish annealing for the purpose of controlling the inhibitor in the plate thickness direction described later. ..
- the shot blasting and / or leveler processing and the step of contacting with the solution may be carried out in a separate step.
- the procedure is mixed up, but first, the solution contact treatment will be described.
- the solution contains one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni (these may be referred to as "Cu and the like" in the present specification), and each of them is contained.
- the total concentration of elements is 0.00001% or more and 1.000% or less in mass%
- the pH is -1.5 or more and less than 7
- the liquid temperature is 15 ° C or more and 100 ° C or less
- the steel plate is used as a solution.
- the immersion time is 5 seconds or more and 200 seconds or less.
- the total concentration of one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni in the solution is less than 0.00001%, the effect of inhibitor control in the plate thickness direction is insufficient. It is not preferable.
- the total concentration of one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni in the solution is more than 1.0000%, the effect of improving magnetism is saturated. , It is not preferable because the cost of the solution increases. Therefore, the total concentration of one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni in the solution is 0.00001% or more and 1.0000% or less.
- the pH of the solution when the pH of the solution is less than ⁇ 1.5, the acidity becomes too strong and it becomes difficult to handle the solution, which is not preferable.
- the pH of the solution is 7 or more, the effect of inhibitor control in the plate thickness direction by the solution contact treatment becomes insufficient, which is not preferable. Therefore, the pH of the solution is -1.5 or more and less than 7.
- the liquid temperature of the solution when the liquid temperature of the solution is less than 15 ° C., the effect of the inhibitor control in the plate thickness direction by the solution contact treatment becomes insufficient, which is not preferable. If the liquid temperature of the solution exceeds 100 ° C., it becomes difficult to handle the solution, which is not preferable. Therefore, the liquid temperature of the solution is 15 ° C. or higher and 100 ° C. or lower.
- the time for the steel sheet to be immersed in the solution in the solution contact treatment is less than 5 seconds, the effect of the inhibitor control in the plate thickness direction by the solution contact treatment becomes insufficient, which is not preferable. If the time for the steel sheet to be immersed in the solution in the solution contact treatment is more than 200 seconds, the equipment becomes long, which is not preferable. Therefore, in the solution contact treatment, the time for the steel sheet to be immersed in the solution is 5 seconds or more and 200 seconds or less.
- the mechanism that enables inhibitor control in the plate thickness direction by solution contact treatment is presumed as follows.
- the solution contains one or more of Cu, Hg, Ag, Pb, Cd, Co, Zn and Ni (these may be referred to as "Cu etc.” in the present specification). Since this element has a very high affinity with S, Se and Te in solution, MnS, MnSe and MnTe (these may be referred to as "MnS etc.” in the present specification) precipitates exposed on the surface of the steel plate. Substitute with Mn to form a compound. This reaction is likely to occur on the surface side of the precipitate such as MnS, which is in contact with the solution.
- the solution penetrates into the steel sheet through those spaces and only MnS etc. exposed on the outermost surface of the steel sheet is used. It is considered that the inhibitor strength is increased by reacting with MnS or the like within a certain depth of the surface layer of the steel sheet.
- the conditions for shot blasting are that the average particle size of the projection material is 0.1 mm or more and 5.0 mm or less, and the projection speed is 10 m / s or more and 150 m / s or less. This introduces fine cracks that allow the solution to penetrate the surface of the steel sheet.
- the blast material projection material
- a general material can be used, and an iron ball having a hardness of about Hv500 may be used. If the average particle size of the projection material is less than 0.1 mm, fine cracks cannot be sufficiently obtained.
- the average particle size of the projection material exceeds 5.0 mm, the shape of the steel sheet is deformed and uniform deformation becomes difficult in cold rolling, and good magnetic characteristics cannot be obtained.
- the projection speed is less than 10 m / s, fine cracks cannot be sufficiently obtained.
- the projection speed exceeds 150 m / s, the shape of the steel sheet is deformed, which makes uniform deformation difficult in cold rolling, and good magnetic characteristics cannot be obtained.
- the shape of the blast material is generally roughly classified into a spherical shape and a square shape.
- the square-shaped blast material has a high grinding ability and can quickly introduce cracks on the surface of the steel sheet.
- either a square-shaped blast material or a spherical-shaped blast material can be applied.
- a square-shaped blast material and a spherical-shaped blast material may be mixed and used.
- leveler processing In addition to shot blasting, leveler processing can be used as a method for introducing defects such as cracks and voids on the surface of the steel sheet.
- a leveler processing process may be used instead of shot blasting, or shot blasting and leveling may be used in combination.
- the leveler ensures the flatness of the steel sheet by bending and unbending along the leveler roll while applying tension to the steel sheet. Defects such as cracks and voids can be introduced on the surface of the steel sheet through bending and unbending with this leveler. Therefore, in the subsequent solution contact treatment, the solution can penetrate into the steel sheet through spaces such as cracks and voids, and the solution can reach not only the outermost surface of the steel sheet but also a range of a certain depth.
- the conditions of the leveler are that the number of times the steel sheet is bent is 2 times or more, the bending angle is 10 degrees or more and 90 degrees or less, and the bending radius is 10 mm or more and 200 mm or less. This introduces fine cracks that allow the solution to penetrate the surface of the steel sheet. If the number of bends is less than 2, fine cracks cannot be sufficiently obtained. Further, when the bending angle is less than 10 degrees, fine cracks cannot be sufficiently obtained. When the bending angle exceeds 90 degrees, the shape of the steel sheet is deformed, which makes uniform deformation difficult in cold rolling, and good magnetic characteristics cannot be obtained. Further, when the bending radius is less than 10 mm, the shape of the steel sheet is deformed, which makes uniform deformation difficult in cold rolling, and good magnetic characteristics cannot be obtained. If the bending radius exceeds 200 mm, fine cracks cannot be sufficiently obtained.
- the mapping intensity ratio of Mn and S is increased in the precipitate particles, and it can be confirmed that the particles are MnS particles, and further, Cu. If the mapping intensity ratio of the above particles is also increased in the vicinity of the surface of the particles, it is presumed that the surface of the precipitate is replaced with Cu.
- the elemental distribution state in the precipitate particles is confirmed by Auger electron spectroscopy. More specifically, by performing elemental analysis while Ar sputtering the surface layer of a precipitate such as MnS at intervals of several nm (typically at 1 nm intervals) by Auger electron spectroscopy, the surface layer of the precipitate particles can be analyzed. , The distribution of constituent elements can be confirmed from the inside. If Cu or the like is detected at a high concentration only in the surface layer portion of the precipitate such as MnS and the concentration of Cu or the like is low inside the precipitate, it is considered that the surface of the precipitate is replaced with Cu or the like. be able to.
- the solution penetrates into the steel sheet through those spaces and is exposed on the outermost surface of the steel sheet. It is considered that it reacts not only with MnS or the like but also with MnS or the like within a certain depth range of the surface layer of the steel sheet.
- the above confirmation method it is possible to confirm at what depth from the surface layer of the steel sheet that the surface of the "MnS or the like” precipitate is replaced with "Cu or the like". From the viewpoint of enhancing the strength of the inhibitor, it is preferable that the surface of the "MnS or the like” precipitate is replaced with "Cu or the like" to a deep range. Typically, it is preferable that the substitution occurs in the range of 10 to 500 ⁇ m from the surface of the steel sheet.
- the equipment and measurement conditions used for SEM, EDS and Auger electron spectroscopy can be appropriately selected according to the measurement target.
- the SEM apparatus used was FE-SEM manufactured by JEOL Ltd., model JEOL7001F, with a WD of 10 mm and an acceleration voltage of 15 kV.
- the Auger electron spectroscopic analyzer was used with FE-AES PHI-700 type manufactured by PHI, electron beam: 10 kV, 10 nA, ion beam: Ar / 2 kV.
- a pickling treatment is performed before the post-process for the purpose of removing scale and cleaning the surface of the steel sheet.
- pickling may be performed before each cold rolling step, and oxidation of the steel plate surface in primary recrystallization annealing is controlled.
- a pickling treatment may be performed before the primary recrystallization annealing, and further, a pickling treatment may be performed before the finish annealing.
- the solution contact treatment may be included in the pickling step of the steel sheet, and the above pH value, liquid temperature, and contact time (pickling time) may be adopted as the pickling conditions.
- the inhibitor (precipitate) heat resistance improving effect and the like by the technique of the present application can be applied to other steel grades, and may be applied to, for example, non-oriented electrical steel sheets.
- the slab components and process conditions are not limited to this.
- the final grain-oriented electrical steel sheet can be manufactured.
- a grain-oriented electrical steel sheet having excellent magnetic characteristics can be manufactured.
- the magnetic flux density B8 value may be further controlled.
- the magnetic flux density B8 value may be 1.91T or more, preferably 1.92T or more, more preferably 1.93T or more, and 1.94T. The above is more preferable, and 1.95T or more is even more preferable.
- the magnetic flux density B8 value is the magnetic flux density when a magnetic field of 800 A / m is applied to the grain-oriented electrical steel sheet at 50 Hz.
- the magnetic flux density B8 value is low, the iron loss value (particularly, hysteresis loss) of the grain-oriented electrical steel sheet becomes large, which is not preferable.
- the upper limit of the magnetic flux density B8 value is not particularly limited, but in reality, it may be, for example, 2.0T.
- the magnetic characteristics of the grain-oriented electrical steel sheet such as the magnetic flux density can be measured by a known method.
- the magnetic properties of grain-oriented electrical steel sheets are measured by using a method based on the Epstein test specified in JIS C2550, or a single plate magnetic property test method (Single Sheet Tester: SST) specified in JIS C2556. be able to.
- SST Single Plate magnetic property test method
- a test piece may be collected so as to have a width of 60 mm and a length of 300 mm, and measurement may be performed in accordance with the single plate magnetic property test method. Further, the obtained result may be multiplied by a correction coefficient so that the same measured value as the method based on the Epstein test can be obtained. In this embodiment, the measurement is performed by a measurement method based on the single plate magnetic property test method.
- the grain-oriented electrical steel sheet thus obtained is processed into rolled iron cores and stacked iron cores when manufacturing transformers.
- the fact that the appearance of the grain-oriented electrical steel sheet is uniform without color unevenness is an important factor for gaining the trust of consumers.
- a color sample is created by dividing the color intensity from white to black into eight equal parts, the area of the steel plate is subdivided into 50 mm ⁇ 50 mm, and the color intensity of each subdivided region is subdivided. Is determined by the color sample divided into eight equal parts, and when a color tone difference of two or more steps occurs between these regions, it may be determined that there is color unevenness.
- a steel plate sample with various color tones and a white and black color sample are scanned at the same time, and the color sample is classified by dividing the brightness from white to black into eight equal parts using commercially available image analysis software. Can be created. By comparing this color sample with the steel sheet, it is possible to analyze whether or not a color difference of two or more steps occurs in an area of the steel sheet of 50 mm ⁇ 50 mm.
- the directional electromagnetic steel sheet according to this embodiment has been described above.
- the grain-oriented electrical steel sheet according to the present embodiment can be manufactured by the method for manufacturing grain-oriented electrical steel sheet according to the present embodiment described above. However, the method is not limited to that method.
- the method for manufacturing the grain-oriented electrical steel sheet and the grain-oriented electrical steel sheet according to the embodiment of the present invention will be described more specifically while showing examples. It should be noted that the examples shown below are merely examples of the grain-oriented electrical steel sheets according to the present embodiment, and the grain-oriented electrical steel sheets according to the present embodiment are not limited to the examples shown below.
- Example 1 ⁇ Manufacturing of grain-oriented electrical steel sheets> First, in terms of mass%, C: 0.04%, Si: 3.3%, Mn: 0.09%, S: 0.002%, Se: 0.001%, Te: 0.001%, acid soluble. A steel ingot containing Al: 0.005% and N: 0.003% and having the balance of Fe and impurities was prepared. The ingot was annealed at 1200 ° C. for 1 hour and then hot-rolled to obtain a hot-rolled steel sheet having a plate thickness of 2.3 mm. The obtained hot-rolled steel sheet is annealed at a maximum temperature of 1000 ° C.
- the obtained cold-rolled steel sheet was subjected to primary recrystallization annealing in a wet hydrogen atmosphere at 850 ° C. for 180 seconds.
- the temperature rising rate was set to the conditions shown in Table 1.
- an annealing separator containing MgO was applied to the surface of the steel sheet after primary recrystallization annealing in the form of an aqueous slurry, and dried.
- finish annealing was performed, and the steel sheet after finish annealing was washed with water.
- an insulating film containing aluminum phosphate and colloidal silica as main components was applied to the surface of the steel sheet, and then flattening annealing was performed for the purpose of baking the insulating film and flattening the steel sheet.
- Directional electrical steel sheet sample after flattening and annealing obtained above is sheared and annealed, and then a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- the B8 value is the magnetic flux density of the grain-oriented steel sheet when the grain-oriented electrical steel sheet is excited at 800 A / m at 50 Hz.
- the average value of 5 samples was used.
- the condition that the magnetic flux density B8 value of the grain-oriented electrical steel sheet is 1.91T or more is good (B)
- the condition that the magnetic flux density B8 value is 1.92T or more is further good (A)
- the condition that the magnetic flux density B8 value is 1.93T or more is extremely good. It was determined that. Then, it was determined that other than the above was impossible (C).
- Table 1 shows the manufacturing conditions, measurement results, and evaluations of the above-mentioned examples of the present invention and comparative examples.
- Example 2 First, it contains C: 0.08%, Si: 3.2%, Mn: 0.08%, S: 0.024%, acid-soluble Al: 0.03%, N: 0.008%, and the balance.
- the conditions for the solution contact treatment after the leveler treatment and the annealing of the hot-rolled plate were carried out under the conditions shown in Table 2.
- the obtained cold-rolled steel sheet was subjected to primary recrystallization annealing in a wet hydrogen atmosphere at 850 ° C. for 180 seconds.
- the temperature rising rate was set to the conditions shown in Table 2.
- an annealing separator containing MgO was applied to the surface of the steel sheet after primary recrystallization annealing in the form of an aqueous slurry, and dried.
- finish annealing was performed, and the steel sheet after finish annealing was washed with water.
- an insulating film containing aluminum phosphate and colloidal silica as main components was applied to the surface of the steel sheet, and then flattening annealing was performed for the purpose of baking the insulating film and flattening the steel sheet.
- Directional electrical steel sheet sample after flattening and annealing obtained above is sheared and annealed, and then a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- the B8 value is the magnetic flux density of the grain-oriented steel sheet when the grain-oriented electrical steel sheet is excited at 800 A / m at 50 Hz.
- the average value of 5 samples was used.
- the condition that the magnetic flux density B8 value of the grain-oriented electrical steel sheet is 1.92T or more is good (B)
- the condition that the magnetic flux density B8 value is 1.93T or more is further good (A)
- the condition that the magnetic flux density B8 value is 1.94T or more is extremely good. It was determined that.
- Table 2 shows the manufacturing conditions, measurement results, and evaluations of the above-mentioned examples of the present invention and comparative examples.
- Example 3 First, in terms of mass%, C: 0.08%, Si: 3.3%, Mn: 0.08%, S: 0.025%, acid-soluble Al: 0.03%, N: 0.008%.
- a steel ingot was prepared which was contained and the balance was composed of the components shown in Table 3 and Fe and impurities. The ingot was annealed at 1350 ° C. for 1 hour and then hot-rolled to obtain a hot-rolled steel sheet having a plate thickness of 2.3 mm. The obtained hot-rolled steel sheet was annealed at a maximum temperature of 1100 ° C. for 140 seconds, subjected to shot blasting and solution contact treatment, and then cold-rolled to obtain a cold-rolled steel sheet having a thickness of 0.23 mm.
- the conditions of the shot blast treatment and the solution contact treatment after annealing the hot-rolled plate are: average particle size of shot: 2 mm, projection speed: 50 m / s, shape: square, Cu concentration in solution: 0.001%.
- the obtained cold-rolled steel sheet was subjected to primary recrystallization annealing in a wet hydrogen atmosphere at 850 ° C. for 180 seconds.
- the heating rate was set under the conditions shown in Table 3.
- an annealing separator containing MgO was applied to the surface of the steel sheet after primary recrystallization annealing in the form of an aqueous slurry, and dried.
- finish annealing was performed, and the steel sheet after finish annealing was washed with water.
- an insulating film containing aluminum phosphate and colloidal silica as main components was applied to the surface of the steel sheet, and then flattening annealing was performed for the purpose of baking the insulating film and flattening the steel sheet.
- Directional electrical steel sheet sample after flattening and annealing obtained above is sheared and annealed, and then a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- a single plate magnetic property measurement method with a sample size of 60 mm x 300 mm (based on the method described in JIS C2556).
- the B8 value is the magnetic flux density of the grain-oriented steel sheet when the grain-oriented electrical steel sheet is excited at 800 A / m at 50 Hz.
- the average value of 5 samples was used.
- the condition that the magnetic flux density B8 value of the grain-oriented electrical steel sheet is 1.92T or more is good (B)
- the condition that the magnetic flux density B8 value is 1.93T or more is further good (A)
- the condition that the magnetic flux density B8 value is 1.94T or more is extremely good.
- S the condition of 1.95T or more was determined to be the highest (SS).
- Table 3 shows the manufacturing conditions, measurement results, and evaluations of the above-mentioned examples of the present invention and comparative examples.
- Example 4 Various intermediate treatments (dew point temperature of atmosphere, residence time of steel plate temperature 700 ° C or higher and 950 ° C or lower) and decarburization annealing (oxygen partial pressure ratio of atmosphere) between temperature rise and decarburization annealing of primary recrystallization annealing are performed.
- decarburization annealing oxygen partial pressure ratio of atmosphere
- a single plate magnetic property measuring method having a sample size of 60 mm ⁇ 300 mm (based on the method described in JIS C2556) is used.
- the B8 value is the magnetic flux density of the grain-oriented steel sheet when the grain-oriented electrical steel sheet is excited at 800 A / m at 50 Hz.
- the average value of 5 samples was used.
- the condition that there is no color difference of two or more stages and the magnetic flux density B8 value of the grain-oriented electrical steel sheet is 1.91T or more is determined to be the best (B). Then, it was determined that other than the above was impossible (C).
- the dew point temperature of the atmosphere is ⁇ 40 ° C. or higher and 0 ° C. or lower
- the residence time of the steel plate temperature is 700 ° C. or higher and 950 ° C. or lower and the residence time is 1 second or longer and 20 seconds or lower.
- the oxygen partial pressure ratio ( PH2O / PH2 ) of the atmosphere is 0.35 or more and 0.60 or less, there is no color difference of two or more steps, and the magnetic flux density of the directional electromagnetic steel plate is B8. It was found that a good determination result (B) with a value of 1.91T or more was obtained.
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Abstract
Description
質量%で、C:0.01%以上0.10%以下、Si:2.5%以上4.5%以下、Mn:0.01%以上0.50%以下、S、SeおよびTeのうち1種または2種以上の合計:0.001%以上0.050%以下、酸可溶性Al:0%超0.05%以下、N:0%超0.015%以下を含有し、残部がFeおよび不純物からなるスラブを加熱して、熱間圧延を施すことで熱延鋼板を得る、あるいは前記熱延鋼板に熱延板焼鈍を施すことで熱延焼鈍板を得る工程と、
前記熱延鋼板あるいは前記熱延焼鈍板に冷間圧延を施すことで冷延鋼板を得る工程と、
前記冷延鋼板に一次再結晶焼鈍を施すことで一次再結晶焼鈍板を得る工程と、
一次再結晶焼鈍板の表面にMgOを含む焼鈍分離剤を塗布した後、仕上焼鈍を施すことで仕上焼鈍板を得る工程と、
前記熱延鋼板、前記熱延焼鈍板、前記冷延鋼板、前記一次再結晶焼鈍板の少なくとも一つの鋼板にショットブラスト処理および溶液と接触する処理を施し、
前記仕上焼鈍板に絶縁被膜を塗布した後、平坦化焼鈍を施す工程と、を含み、
前記ショットブラスト処理では、投射材の平均粒径が0.1mm以上5.0mm以下であり、投射速度は10m/s以上150m/s以下であり、
前記溶液がCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうちから1種または2種以上を含有し、各元素の濃度の合計が0.00001%以上1.0000%以下であり、pHが―1.5以上7未満であり、液温は15℃以上100℃以下であり、前記鋼板が前記溶液に浸漬される時間は5秒以上200秒以下であることを特徴とする方向性電磁鋼板の製造方法、が提供される。
上述のショットブラスト処理に代えて、またはショットブラスト処理に加えて、レベラー加工処理を行なってもよく、
前記レベラー加工処理では、前記熱延鋼板の曲げ回数が2回以上であり、曲げ角度が10度以上90度以下であり、曲げ半径が10mm以上200mm以下であることを特徴とする方向性電磁鋼板の製造方法、が提供される。
前記一次再結晶焼鈍の急速昇温において、550℃~700℃の温度域の平均昇温速度が、100℃/s以上3000℃/s以下であることを特徴とする方向性電磁鋼板の製造方法、が提供される。
前記スラブが、前記Feの一部に替えて、Cu:1.0%以下、Sn:1.0%以下、Ni:1.0%以下、Cr:1.0%以下、Sb:1.0%以下、Bi:1.0%以下からなる群から選ばれる1種または2種以上を含有するものであることを特徴とする、方向性電磁鋼板の製造方法、が提供される。
前記一次再結晶焼鈍は、昇温する工程と、昇温から脱炭焼鈍の間に中間処理する工程と、脱炭焼鈍する工程を含み、
前記中間処理では、雰囲気の露点温度が-40℃以上0℃以下かつ鋼板温度700℃以上950℃以下の滞留時間が1秒以上20秒以下であり、
前記脱炭焼鈍では、雰囲気の酸素分圧比(PH2O/PH2)が0.35以上0.60以下であることを特徴とする方向性電磁鋼板の製造方法、が提供される。
本発明者らは、方向性電磁鋼板の磁気特性を向上させるために、方向性電磁鋼板の製造方法について鋭意検討を行った結果、以下の知見を見出した。
さらに、一次再結晶焼鈍の昇温過程において急速加熱処理を施すことで表層近傍のGoss方位粒を増加することで、磁気特性をさらに向上できることを見出した。
また、スラブに添加元素を付加して、二次結晶を安定化させることで、さらに磁気特性を向上できることを見出した。
さらに、上記のMnS等の表層のMnがCu等に置換する現象は、最終製品の色むらを生じることがあるが、一次再結晶焼鈍(急速加熱処理と中間処理と脱炭焼鈍)の中間処理における雰囲気や温度条件および脱炭焼鈍における雰囲気条件を制御して改善することで解消できることを見出した。
前記熱延鋼板あるいは前記熱延焼鈍板に冷間圧延を施すことで冷延鋼板を得る工程と、
前記冷延鋼板に一次再結晶焼鈍を施すことで一次再結晶焼鈍板を得る工程と、
一次再結晶焼鈍板の表面にMgOを含む焼鈍分離剤を塗布した後、仕上焼鈍を施すことで仕上焼鈍板を得る工程と、
前記仕上焼鈍板に絶縁被膜を塗布した後、平坦化焼鈍を施す工程と、を含み、
前記熱延鋼板、前記熱延焼鈍板、前記冷延鋼板、前記一次再結晶焼鈍板の少なくとも一つの鋼板にショットブラスト処理および溶液と接触する処理を施し、
前記ショットブラスト処理では、投射材の平均粒径が0.1mm以上5.0mm以下であり、投射速度は10m/s以上150m/s以下であり、
前記溶液がCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうちから1種または2種以上を含有し、各元素の濃度の合計が0.00001%以上1.0000%以下であり、pHが―1.5以上7未満であり、液温は15℃以上100℃以下であり、前記鋼板が前記溶液に浸漬される時間は5秒以上200秒以下である。
前記レベラー加工処理では、前記鋼板の曲げ回数が2回以上であり、曲げ角度が10度以上90度以下であり、曲げ半径が10mm以上200mm以下である。
前記中間処理では、雰囲気の露点温度が-40℃以上0℃以下かつ鋼板温度700℃以上950℃以下の滞留時間が1秒以上20秒以下であり、
前記脱炭焼鈍では、雰囲気の酸素分圧比(PH2O/PH2)が0.35以上0.60以下である。
まず、本実施形態に係る方向性電磁鋼板に用いられるスラブの成分組成について説明する。なお、以下では特に断りのない限り、「%」との表記は「質量%」を表わすものとする。また、以下で説明する元素以外のスラブの残部は、Feおよび不純物である。ここで、不純物とは、原材料に含まれる成分、または製造の過程で混入する成分であって、意図的に鋼板に含有させたものではない成分を指す。また、方向性電磁鋼板の素材であるスラブの化学組成は基本的には方向性電磁鋼板の組成に準じたものになる。しかし、一般的な方向性電磁鋼板の製造においては製造過程で脱炭焼鈍および純化焼鈍により含有元素の一部が系外に排出されるため、素材であるスラブと最終製品である方向性電磁鋼板の化学組成は異なるものとなる。方向性電磁鋼板の特性を所望のものになるように、製造過程での脱炭焼鈍および純化焼鈍の影響等を考慮して、スラブ組成を適宜調整可能である。
続いて、スラブを加熱して熱間圧延を施すことで熱延鋼板に加工される。スラブ加熱温度は、特に限定されない。スラブ中のインヒビター成分を完全固溶させる場合は、例えば、1280℃以上に加熱してもよい。なお、このときのスラブの加熱温度の上限値は、特に定めないが、設備保護の観点から1450℃が好ましく、例えば、スラブの加熱温度は、1280℃以上1450℃以下であってもよい。一方、スラブ中のインヒビター成分を完全固溶させない場合は、例えば、スラブ加熱温度を1280℃未満としてもよい。この場合、熱間圧延工程または熱延板焼鈍工程から仕上焼鈍工程のいずれかの工程において、鋼板に窒化処理を施してもよい。
熱延鋼板に熱延板焼鈍を施して熱延焼鈍板を得てもよい。熱延板焼鈍を施す場合、鋼板形状がより良好になるため、後工程の冷間圧延にて鋼板が破断する可能性を軽減することができる。
続いて、得られた熱延鋼板または熱延焼鈍板は、1回の冷間圧延、または中間焼鈍を挟んだ複数回の冷間圧延にて圧延されることで、冷延鋼板に加工される。なお、中間焼鈍および/または酸洗を挟んだ複数回の冷間圧延にて圧延する場合、前段の熱延板焼鈍を省略することも可能である。冷間圧延におけるロール摩耗を軽減する観点からは、各冷間圧延工程の前に、酸洗処理が施されることが好ましい。また、熱延板焼鈍および中間焼鈍の両方を施しても構わない。
次に、冷延鋼板は、昇温された後、脱炭焼鈍される。これらの過程は、一次再結晶焼鈍とも称され、連続して行われることが好ましい。一次再結晶焼鈍の昇温を急速昇温とすることで、冷延鋼板では、二次再結晶前のGoss方位粒を増加させることが可能となり、二次再結晶過程において、より理想Goss方位に近い方位粒が二次再結晶することが期待される。
本発明では、一次再結晶焼鈍における昇温過程において、550℃~700℃の間の平均昇温速度を、100℃/s以上3000℃/s以下の急速としてもよい。これにより、冷延鋼板の二次再結晶前のGoss方位粒を増加させることができ、最終的な方向性電磁鋼板の磁束密度を向上することができる。急速昇温の温度範囲は、550℃~700℃である。急速昇温の開始温度が550℃超である場合、鋼板中で転位の回復が大きく進行し、Goss方位粒以外の方位粒の一次再結晶が開始してしまうため、Goss方位粒増加効果が減じるので好ましくない。急速昇温の終了温度が700℃未満である場合、Goss方位粒の一次再結晶が完了する前に、他の方位粒の一次再結晶が完了してしまうため、Goss方位粒増加効果が減じるので好ましくない。
また、本発明の一態様では、一次再結晶焼鈍における昇温工程と脱炭焼鈍工程の間に、中間処理工程を備え、中間処理工程における雰囲気の露点温度は、-40℃以上0℃以下であり、かつ鋼板温度700℃以上950℃以下の滞留時間は、1秒以上20秒以下としてもよい。
中間処理における鋼板温度700℃以上950℃以下の滞留時間が1秒未満である場合、引き続く脱炭焼鈍において酸化膜形成が不均一となり、最終製品として得られる方向性電磁鋼板の外観に色むらが生じて好ましくない。中間処理における鋼板温度700℃以上950℃以下の滞留時間の上限は、特に限定されないが、20秒超である場合は設備が長大となるので好ましくない。
中間処理における露点温度が-40℃未満の場合、特にCu、Hg、Ag、Pb、Cd、Co、ZnまたはNiが局在する箇所において、中間処理における酸化膜の形成量が不十分となるため、好ましくない。一方、中間処理における露点温度が0℃超の場合、中間処理において外部酸化型のシリカ膜が形成されてしまい、引き続く脱炭焼鈍において内部酸化の進行が抑制されて酸化膜が薄くなってしまうため、Cu、Hg、Ag、Pb、Cd、Co、ZnまたはNiが局在する箇所における酸化量不足が顕在化して、色むらが最終製品まで残存してしまうと推定される。
中間処理における鋼板温度700℃以上950℃以下の滞留時間が1秒未満である場合も、中間処理における酸化膜の形成量が不十分となるため、好ましくない。滞留時間が20秒超である場合、設備が長大となるので好ましくない。
次に、冷延鋼板は脱炭焼鈍される。脱炭焼鈍は、脱炭性の観点から、水素および窒素含有の湿潤雰囲気中において、900℃以下の温度で実施されてもよい。ここで、脱炭性を阻害しないために、脱炭焼鈍の雰囲気の酸素分圧比、すなわち雰囲気中の水蒸気分圧PH2Oと、水素分圧PH2との比PH2O/PH2を、0.35以上にしてもよい。
その後、一次再結晶焼鈍後の冷延鋼板に仕上焼鈍を施す。その際、鋼板間の焼き付き防止や、一次被膜形成や、二次再結晶挙動制御などを目的としてMgOを主成分とする焼鈍分離剤が仕上焼鈍前に塗布されてもよい。前記焼鈍分離剤は、一般的に水スラリーの状態で鋼板表面に塗布、乾燥されるが、静電塗布法などを用いてもよい。
続いて、仕上焼鈍の後、鋼板へ絶縁性および張力付与を目的として、例えば、リン酸アルミニウムまたはコロイダルシリカなどを主成分とした絶縁被膜が鋼板の表面に塗布される。その後、絶縁被膜の焼付、および仕上焼鈍による鋼板形状の平坦化を目的として、平坦化焼鈍が施される。なお、鋼板に対して絶縁性および張力が付与されるのであれば、絶縁被膜の成分は特に限定されない。なお、本実施形態では、需要家の目的によっては、方向性電磁鋼板に磁区制御処理が施されてもよいことは言うまでもない。
本工程では、熱延鋼板、熱延焼鈍板、冷延鋼板、一次再結晶焼鈍板の少なくとも一つの鋼板をショットブラストおよび/またはレベラー加工処理を施した上で溶液に浸漬する。溶液と接触させる処理(以下、「溶液接触処理」と称することもある)は、後述する板厚方向インヒビター制御のために、熱間圧延の後、仕上焼鈍の前に、少なくとも一回施される。なお、ショットブラストおよび/またはレベラー加工処理と溶液と接触させる工程は、別工程で実施されてもよい。
手順は前後するが、まず、溶液接触処理について説明する。当該溶液は、Cu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうちから1種または2種以上(本明細書においてこれらを「Cu等」と称することがある)を含有し、各元素の濃度の合計が質量%で0.00001%以上1.0000%以下であり、pHが―1.5以上7未満であり、液温は15℃以上100℃以下であり、鋼板が溶液に浸漬される時間は5秒以上200秒以下である。
溶液のCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうち1種または2種以上の濃度の合計が0.00001%未満である場合、板厚方向のインヒビター制御の効果が不十分となり好ましくない。溶液のCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうち1種または2種以上の濃度の合計が1.0000%超である場合、磁性向上の効果が飽和することに加えて、溶液のコストが増大するので好ましくない。したがって、溶液のCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうち1種または2種以上の濃度の合計は、0.00001%以上1.0000%以下である。
また、溶液のpHが―1.5未満である場合、酸性が強くなり過ぎて溶液の取扱いが困難となるので好ましくない。溶液のpHが7以上である場合、溶液接触処理による板厚方向のインヒビター制御の効果が不十分となり好ましくない。したがって、溶液のpHは、-1.5以上7未満である。
また、溶液の液温が15℃未満である場合、溶液接触処理による板厚方向のインヒビター制御の効果が不十分となり好ましくない。溶液の液温が100℃超である場合、溶液の取扱いが困難となるので好ましくない。したがって、溶液の液温は15℃以上100℃以下である。
また、溶液接触処理において鋼板が溶液に浸漬される時間が5秒未満である場合、溶液接触処理による板厚方向のインヒビター制御の効果が不十分となり好ましくない。溶液接触処理において鋼板が溶液に浸漬される時間が200秒超である場合、設備が長大となるので好ましくない。したがって、溶液接触処理において鋼板が溶液に浸漬される時間は5秒以上200秒以下である。
ショットブラスト処理等の処理によって鋼板表面にひび割れやボイド等の欠陥を導入して、その後の溶液接触処理で、溶液はそれらの空間を通って鋼板内に浸入して、溶液が鋼板の最表面だけでなく、一定深さの範囲までに及ぶようにする。前述した溶液処理によって、析出物であり、インヒビターとして作用するMnS、MnSeおよびMnTe(本明細書においてこれらを「MnS等」と称することがある)の表面のMnをCu等で置換することで、インヒビターの耐熱性を高めることができる。したがって、ショットブラストによって、鋼板の最表面だけでなく、鋼板の一定深さまで溶液を浸透させ、そこに存在するMnS等のインヒビターの強度を強化することができる。
鋼板表面にひび割れやボイド等の欠陥を導入する方法としては、ショットブラスト以外にも、レベラー加工処理を用いることができる。ショットブラストの代わりにレベラー加工処理を用いてもよく、また、ショットブラストとレベラーを併用してもよい。
レベラーは、鋼板に張力を付与しながらレベラーロールに沿って、曲げ、曲げ戻しを行うことで、鋼板の平坦性を確保するものである。このレベラーでの曲げ、曲げ戻しを通じて、鋼板表面にひび割れやボイド等の欠陥を導入できる。したがって、その後の溶液接触処理で、溶液はひび割れやボイド等の空間を通って鋼板内に浸入して、溶液が鋼板の最表面だけでなく、一定深さの範囲までに及ぶことができる。
MnS等の析出物の表面がCu等で置換されていることの確認手法について説明する。
まず、確認対象となる鋼板試料を鏡面研磨し、SEM-EDX観察を行う。SEMによる観察画像で、MnS等の析出物の存在が確認できる。その観察画像に、Cu等、例えば、Mn,S,CuのEDXの元素マッピングと強度比を重ね合わせていく。これにより、当該析出物粒子の構成元素を確認することができる。典型的な例では、析出物粒子とその近傍を観察すると、析出物粒子の部分において、MnとSのマッピング強度比が上昇しており、当該粒子がMnS粒子であることが確認でき、さらにCuのマッピング強度比も当該粒子の表面近傍部分において上昇していれば、析出物の表面がCuで置換されていることが推定される。
これに応じて、溶液接触処理が、鋼板の酸洗工程に含まれてもよく、その酸洗条件として上記のpH値、液温、接触時間(酸洗時間)を採用してもよい。なお、本願技術によるインヒビター(析出物)耐熱性向上効果等は、他鋼種へも適用可能であり、例えば、無方向性電磁鋼板に適用されても構わない。他鋼種に適用される場合は、スラブ成分や工程条件は、この限りではない。
<方向性電磁鋼板の製造>
まず、質量%で、C:0.04%、Si:3.3%、Mn:0.09%、S:0.002%、Se:0.001%、Te:0.001%、酸可溶性Al:0.005%、N:0.003%を含有し、残部がFeおよび不純物からなる鋼塊を作製した。該鋼塊を1200℃にて1時間焼鈍した後、熱間圧延を施すことで、板厚2.3mmの熱延鋼板を得た。得られた熱延鋼板を最高温度1000℃にて140秒間焼鈍し、酸洗を施した後に、中間焼鈍およびショットブラスト処理および溶液接触処理を挟む2回の冷間圧延を施すことで、板厚0.23mmの冷延鋼板を得た。ここで、中間焼鈍後のショットブラスト処理および溶液接触処理条件は、表1に示す条件で行った。
まず、C:0.08%、Si:3.2%、Mn:0.08%、S:0.024%、酸可溶性Al:0.03%、N:0.008%を含有し、残部がFeおよび不純物からなる鋼塊を作製した。該鋼塊を1350℃にて1時間焼鈍した後、熱間圧延を施すことで、板厚2.3mmの熱延鋼板を得た。得られた熱延鋼板を最高温度1100℃にて140秒間焼鈍し、レベラー処理および溶液接触処理を施した後に冷間圧延を施すことで、板厚0.23mmの冷延鋼板を得た。ここで、レベラー処理および熱延板焼鈍後の溶液接触処理条件は、表2に示す条件で行った。
まず、質量%で、C:0.08%、Si:3.3%、Mn:0.08%、S:0.025%、酸可溶性Al:0.03%、N:0.008%を含有し、残部が表3に示す成分とFeおよび不純物からなる鋼塊を作製した。該鋼塊を1350℃にて1時間焼鈍した後、熱間圧延を施すことで、板厚2.3mmの熱延鋼板を得た。得られた熱延鋼板を最高温度1100℃にて140秒間焼鈍し、ショットブラスト処理および溶液接触処理を施した後に冷間圧延を施すことで、板厚0.23mmの冷延鋼板を得た。ここで、熱延板焼鈍後のショットブラスト処理および溶液接触処理の条件は、ショットの平均粒径:2mm、投射速度:50m/s、形状:角状、溶液中のCu濃度:0.001%、溶液(ベース):塩酸、溶液のpH:3、溶液温度:70℃、溶液と鋼板の接触時間:30秒とした。
1次再結晶焼鈍の昇温から脱炭焼鈍の間の中間処理(雰囲気の露点温度、鋼板温度700℃以上950℃以下の滞留時間)および脱炭焼鈍(雰囲気の酸素分圧比)を、様々な条件を用いたことを除いて、実施例1~3の本発明例と同様の条件で方向性電磁鋼板を製造した。
脱炭焼鈍では、雰囲気の酸素分圧比(PH2O/PH2)が0.35以上0.60以下である場合に、2段階以上の色調差がなく、かつ、方向性電磁鋼板の磁束密度B8値が1.91T以上となる、良好な判定結果(B)が得られることが分かった。
Claims (5)
- 質量%で、C:0.01%以上0.10%以下、Si:2.5%以上4.5%以下、Mn:0.01%以上0.50%以下、S、SeおよびTeのうち1種または2種以上の合計:0.001%以上0.050%以下、酸可溶性Al:0%超0.05%以下、N:0%超0.015%以下を含有し、残部がFeおよび不純物からなるスラブを加熱して、熱間圧延を施すことで熱延鋼板を得る、あるいは前記熱延鋼板に熱延板焼鈍を施すことで熱延焼鈍板を得る工程と、
前記熱延鋼板あるいは前記熱延焼鈍板に冷間圧延を施すことで冷延鋼板を得る工程と、
前記冷延鋼板に一次再結晶焼鈍を施すことで一次再結晶焼鈍板を得る工程と、
一次再結晶焼鈍板の表面にMgOを含む焼鈍分離剤を塗布した後、仕上焼鈍を施すことで仕上焼鈍板を得る工程と、
前記仕上焼鈍板に絶縁被膜を塗布した後、平坦化焼鈍を施す工程と、を含み、
前記熱延鋼板、前記熱延焼鈍板、前記冷延鋼板、前記一次再結晶焼鈍板の少なくとも一つの鋼板にショットブラスト処理および溶液と接触する処理を施し、
前記ショットブラスト処理では、投射材の平均粒径が0.1mm以上5.0mm以下であり、投射速度は10m/s以上150m/s以下であり、
前記溶液がCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうちから1種または2種以上を含有し、各元素の濃度の合計が0.00001%以上1.0000%以下であり、pHが―1.5以上7未満であり、液温は15℃以上100℃以下であり、前記鋼板が前記溶液に浸漬される時間は5秒以上200秒以下であることを特徴とする方向性電磁鋼板の製造方法。 - 質量%で、C:0.01%以上0.10%以下、Si:2.5%以上4.5%以下、Mn:0.01%以上0.50%以下、S、SeおよびTeのうち1種または2種以上の合計:0.001%以上0.050%以下、酸可溶性Al:0%超0.05%以下、N:0%超0.015%以下を含有し、残部がFeおよび不純物からなるスラブを加熱して、熱間圧延を施すことで熱延鋼板を得る、あるいは前記熱延鋼板に熱延板焼鈍を施すことで熱延焼鈍板を得る工程と、
前記熱延鋼板あるいは前記熱延焼鈍板に冷間圧延を施すことで冷延鋼板を得る工程と、
前記冷延鋼板に一次再結晶焼鈍を施すことで一次再結晶焼鈍板を得る工程と、
一次再結晶焼鈍板の表面にMgOを含む焼鈍分離剤を塗布した後、仕上焼鈍を施すことで仕上焼鈍板を得る工程と、
前記仕上焼鈍板に絶縁被膜を塗布した後、平坦化焼鈍を施す工程と、を含み、
前記熱延鋼板、前記熱延焼鈍板、前記冷延鋼板、前記一次再結晶焼鈍板の少なくとも一つの鋼板にレベラー加工処理および溶液と接触する処理を施し、
前記レベラー加工処理では、前記鋼板の曲げ回数が2回以上であり、曲げ角度が10度以上90度以下であり、曲げ半径が10mm以上200mm以下であり、
前記溶液がCu、Hg、Ag、Pb、Cd、Co、ZnおよびNiのうちから1種または2種以上を含有し、各元素の濃度の合計が0.00001%以上1.0000%以下であり、pHが―1.5以上7未満であり、液温は15℃以上100℃以下であり、前記鋼板が前記溶液に浸漬される時間は5秒以上200秒以下であることを特徴とする方向性電磁鋼板の製造方法。 - 前記一次再結晶焼鈍の急速昇温において、550℃~700℃の温度域の平均昇温速度が、100℃/s以上3000℃/s以下であることを特徴とする、請求項1または2に記載の方向性電磁鋼板の製造方法。
- 前記スラブが、前記Feの一部に替えて、Cu:1.0%以下、Sn:1.0%以下、Ni:1.0%以下、Cr:1.0%以下、Sb:1.0%以下、Bi:1.0%以下からなる群から選ばれる1種または2種以上を含有するものであることを特徴とする請求項1~3のいずれか1項に記載の方向性電磁鋼板の製造方法。
- 前記一次再結晶焼鈍は、昇温する工程と、昇温から脱炭焼鈍の間に中間処理する工程と、脱炭焼鈍する工程を含み、
前記中間処理では、雰囲気の露点温度が-40℃以上0℃以下かつ鋼板温度700℃以上950℃以下の滞留時間が1秒以上20秒以下であり、
前記脱炭焼鈍では、雰囲気の酸素分圧比(PH2O/PH2)が0.35以上0.60以下であることを特徴とする請求項1~4のいずれか1項に記載の方向性電磁鋼板の製造方法。
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KR102140991B1 (ko) * | 2016-03-09 | 2020-08-04 | 제이에프이 스틸 가부시키가이샤 | 방향성 전자 강판의 제조 방법 |
JP7106910B2 (ja) * | 2018-03-20 | 2022-07-27 | 日本製鉄株式会社 | 方向性電磁鋼板の製造方法 |
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2021
- 2021-06-23 US US18/009,919 patent/US20230243013A1/en active Pending
- 2021-06-23 EP EP21828514.6A patent/EP4174192A4/en active Pending
- 2021-06-23 CN CN202180014834.6A patent/CN115135780A/zh active Pending
- 2021-06-23 KR KR1020227030477A patent/KR20220134013A/ko not_active Application Discontinuation
- 2021-06-23 WO PCT/JP2021/023783 patent/WO2021261517A1/ja unknown
- 2021-06-23 BR BR112022024371A patent/BR112022024371A2/pt unknown
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Also Published As
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US20230243013A1 (en) | 2023-08-03 |
KR20220134013A (ko) | 2022-10-05 |
EP4174192A4 (en) | 2024-07-03 |
EP4174192A1 (en) | 2023-05-03 |
CN115135780A (zh) | 2022-09-30 |
BR112022024371A2 (pt) | 2022-12-27 |
JPWO2021261517A1 (ja) | 2021-12-30 |
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