WO2015170755A1 - 低鉄損で低磁歪の方向性電磁鋼板 - Google Patents
低鉄損で低磁歪の方向性電磁鋼板 Download PDFInfo
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- WO2015170755A1 WO2015170755A1 PCT/JP2015/063357 JP2015063357W WO2015170755A1 WO 2015170755 A1 WO2015170755 A1 WO 2015170755A1 JP 2015063357 W JP2015063357 W JP 2015063357W WO 2015170755 A1 WO2015170755 A1 WO 2015170755A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/08—Devices involving relative movement between laser beam and workpiece
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/206—Laser sealing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D10/00—Modifying the physical properties by methods other than heat treatment or deformation
- C21D10/005—Modifying the physical properties by methods other than heat treatment or deformation by laser shock processing
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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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- 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 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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- 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 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
- C21D8/1288—Application of a tension-inducing coating
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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
- C21D8/1294—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a localized treatment
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
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- 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 used for a core such as a transformer, and in particular, a grain-oriented electrical steel sheet with low iron loss and low magnetostriction that contributes not only to lowering iron loss of an iron core but also to lowering noise. It is about.
- This application claims priority on May 9, 2014 based on Japanese Patent Application No. 2014-97685 for which it applied to Japan, and uses the content here.
- the grain-oriented electrical steel sheet is mainly used for a static inductor represented by a transformer.
- the characteristics to be satisfied include low iron loss, easy excitation, and low magnetostriction. Since the transformer is continuously energized over a long period of time from installation to disposal and continues to generate energy loss, it is required that iron loss is particularly low among these characteristics.
- the grain-oriented electrical steel sheet used in the manufacturing process is required to have low magnetostriction as well as low iron loss.
- Laser irradiation for reducing iron loss is effective in subdividing the magnetic domain width by introducing residual strain, but is known to be a source of magnetostriction. Therefore, when performing magnetic domain control by irradiating a grain-oriented electrical steel sheet with a coating formed thereon, the magnetostriction is reduced by adjusting the laser irradiation conditions and the coating tension to achieve both low iron loss and low magnetostriction. Techniques for this purpose are disclosed in Patent Documents 1 to 4.
- Patent Document 1 as the factors that determine magnetostriction, the tension of the primary coating, the tension of the tension insulating coating, and the application of minute strain due to laser irradiation are very important. By controlling these factors, low noise can be achieved. It is disclosed that a grain-oriented electrical steel sheet having a magnetostrictive characteristic for the purpose and having a low iron loss can be provided.
- a pulse is applied so that the tension applied to the total steel plate by the primary coating and the secondary coating applied thereafter is 1 to 8 MPa, and the heat input per unit area of the steel plate is 1 to 2 mJ / mm 2. It is disclosed that laser irradiation is performed, or that the tension is set to 14 MPa or more and the heat input amount is set to 1.5 to 3 mJ / mm 2 .
- Patent Document 2 when a magnetic domain subdivision by laser irradiation is performed on a grain oriented electrical steel sheet having a forsterite film and a tension coating, the film is damaged and the magnetostrictive characteristics are prevented from deteriorating. Therefore, the total tension A in the rolling direction applied to the steel sheet by the forsterite coating and the tension coating is 10.0 MPa or more, the total tension B in the direction perpendicular to the rolling direction is 5.0 MPa or more, and the total A grain-oriented electrical steel sheet having a tension A / B ratio A / B of 1.0 to 5.0 is disclosed.
- Patent Document 3 when performing magnetic domain control by irradiating a directional electromagnetic steel sheet with a laser, the solidified layer thickness of the laser irradiation part is set to a maximum of 4 ⁇ m so that strain is introduced only in a narrow range in the rolling direction. Accordingly, a technique for suppressing magnetostriction deformation at the same time as reducing iron loss is disclosed.
- Patent Document 4 the amount of primary coating and the amount of tension insulating coating are detected before laser irradiation is performed on the grain-oriented electrical steel sheet, and laser irradiation is performed under appropriate irradiation conditions according to these detection amounts. Discloses a technique for reducing magnetostriction and transformer noise at the same time as reducing iron loss.
- Japanese Unexamined Patent Publication No. 2002-356750 Japanese Unexamined Patent Publication No. 2012-031498 Japanese Unexamined Patent Publication No. 2007-002334 Japanese Unexamined Patent Publication No. 2012-031519
- an object of the present invention is to provide a grain-oriented electrical steel sheet that achieves both low iron loss and low magnetostriction.
- the iron loss of grain-oriented electrical steel sheets is reduced by minimizing the sum of eddy current loss and hysteresis loss. And this eddy current loss and hysteresis loss change complicatedly with respect to various material parameters.
- the magnetostrictive deformation of the grain-oriented electrical steel sheet also changes in a complicated manner with respect to various material parameters.
- the steel sheet base material is stressed by the coating (tensile insulation coating and primary coating (glass coating)) applied to the grain-oriented electrical steel sheet, but stress is also applied to the steel sheet base material by laser irradiation for magnetic domain control. Will be added.
- the present inventors have found that there are ranges of coating tension and laser applied stress that minimize the above-described iron loss and magnetostriction in a well-balanced manner depending on the degree of influence of these stress distributions. And the said stress was evaluated by the change of the curvature amount of a grain-oriented electrical steel sheet, and the range where a magnetostriction becomes optimal was discovered.
- a grain-oriented electrical steel sheet according to an aspect of the present invention includes a steel plate base material, a primary coating formed on a surface of the steel plate base material, and a tension insulating coating formed on the surface of the primary coating.
- the magnetic domain is controlled by irradiating a laser beam on the tension insulating coating.
- a strip-shaped sample having a length in the direction parallel to the rolling direction of the grain-oriented electrical steel sheet of 300 mm and a length in the direction parallel to the sheet width direction of 60 mm is taken from the grain-oriented electrical steel sheet, and at least the sample The sample after removing a range from the surface of the tensile insulating coating to a depth position of 5 ⁇ m closer to the steel plate base than the interface between the steel plate base and the primary coating by pickling one side When the amount of warpage is measured, the amount of warpage satisfies the following formulas A and B.
- t / d p may be 0.1 or more and 3.0 or less.
- t / d p may be 0.1 or more and 1.5 or less.
- t / d p may be 0.1 or more and 1.0 or less.
- an average film thickness of the tensile insulating coating may be not less than 0.5 ⁇ m and not more than 4.5 ⁇ m.
- a total tension applied to the steel sheet base material by the primary coating and the tension insulating coating is 1 MPa or more and 10 MPa or less. It may be.
- a grain-oriented electrical steel sheet excellent in both iron loss and magnetostriction can be provided.
- the grain-oriented electrical steel sheet in which a primary coating (glass coating) and a tension insulating coating are formed on both surfaces, the grain-oriented electrical steel sheet that has been subjected to magnetic domain fragmentation treatment by laser irradiation on one surface depends on the coating tension. Stress and stress due to laser irradiation are added. It is well known that magnetostriction is greatly influenced by the stress applied to the electrical steel sheet. The degree of influence on magnetostriction changes depending on the magnitudes of the two stresses described above.
- the present inventors examined in further detail the degree of influence of the film tension composed of the primary film and the tension insulating film on the magnetostriction and the degree of influence of the stress caused by laser irradiation on the magnetostriction.
- the stress due to the film tension and the stress due to the laser irradiation were evaluated by the warpage amount of the grain-oriented electrical steel sheet, and the change in the warpage amount based on the stress due to the film tension and the warpage amount based on the stress due to the film tension and the stress due to the laser irradiation It has been found that there is a range in which magnetostriction is optimal by adjusting the change.
- the cold rolled steel sheet containing 3.2% by mass of Si and rolled to a sheet thickness of 0.23 mm was subjected to decarburization annealing and primary recrystallization annealing while changing the dew point. Then, finish annealing was performed in the state which applied the annealing separation agent which has MgO as a main component on the steel plate surface, and the grain-oriented electrical steel plate material which has the primary coat (glass coat) of various thickness was obtained. Next, a number of samples were cut out from the obtained grain-oriented electrical steel sheet material, and a coating treatment liquid containing colloidal silica and aluminum phosphate was applied. The coating amount of the coating treatment liquid was changed for each sample.
- the sample coated with the coating treatment liquid was baked at a temperature of 800 ° C. to form tension insulating coatings (secondary coatings) having various thicknesses.
- tension insulating coatings secondary coatings
- one domain of each sample was subjected to a magnetic domain subdivision process in which a continuous wave laser with different irradiation energy (heat input amount) was irradiated.
- a number of grain-oriented electrical steel sheets having different coating film forming conditions and laser irradiation conditions were obtained.
- the iron loss W 17/50 is an iron loss at 50 Hz at an excitation magnetic flux density of 1.7 T, and was measured using a single plate magnetic tester (SST).
- a strip-like sample having a length in the direction parallel to the rolling direction of 300 mm and a length in the direction parallel to the plate width direction of 60 mm is taken from the grain-oriented electrical steel sheet, and one side of the sample or the sample Both sides of the substrate were pickled in the following manners a to c.
- the range from the surface of the tension insulating coating to the depth position of 5 ⁇ m was removed from the interface between the steel plate base material and the primary coating to the steel plate base material side. Thereafter, the amount of warpage of each sample tip was measured.
- b. Pickling only one side of the sample opposite the laser-irradiated side c. As shown in FIG.
- the amount of warpage after pickling both sides of the sample was placed vertically with 30 mm at one end in the longitudinal direction of the sample sandwiched between clamps, and the amount of displacement at one end on the opposite side (
- the amount of warpage was determined by measurement.
- the warp in the same direction as the pickled surface is set to a positive value in the measurement of the mode of a and the mode of b, and the measurement is performed in the same direction as the mode of a in the measurement of the mode of c. Warpage was taken as a positive value.
- the iron loss W 17/50 is 0.75 W / kg or less, and the magnetostriction ⁇ 0-p without load stress is 0.25 ⁇ 10 ⁇ 6 or less.
- G Good
- iron loss W 17/50 is more than 0.75 W / kg
- magnetostriction ⁇ 0-p is more than 0.25 ⁇ 10 ⁇ 6
- F Air
- iron loss W 17/50 is more than 0.75 W / kg
- magnetostriction ⁇ 0-p is 0.25 ⁇ 10 ⁇
- the case of more than 6 is expressed as NG (Not Good) because neither the low iron loss nor the low magnetostriction is satisfied.
- any of the [Delta] S C and [Delta] S L is, ⁇ S C : 15000-35000 ⁇ m, ⁇ S L : 900 to 14000 ⁇ m
- ⁇ S C 15000-35000 ⁇ m
- ⁇ S L 900 to 14000 ⁇ m
- the present embodiment has been made as a result of the above studies, and the requirements and preferred requirements of the present embodiment will be further described below.
- it has a primary coating (typically forsterite coating) formed on both surfaces of the steel plate base material in finish annealing in the manufacturing process, and a tension insulating coating applied and baked thereon, A grain-oriented electrical steel sheet whose magnetic domain is controlled by irradiating a laser on one side is targeted.
- a tension insulating coating is formed on a grain-oriented electrical steel sheet having a mirror surface, the idea of this embodiment is impaired. is not.
- a silicon steel material containing 1.0 to 4.0% by mass of Si is subjected to hot rolling and cold rolling to a steel plate having a predetermined thickness, and then decarburized annealing and annealing separation. What is necessary is just to be manufactured through application
- a film is collected from the grain-oriented electrical steel sheet by adjusting the film formation conditions of the primary coating and the tension insulating film and the laser irradiation conditions.
- [Delta] S C that is defined by S A -S C is in the range of 15000 ⁇ 35000 ⁇ m, so that [Delta] S L defined by S B + S C is in the range of 900 ⁇ 14000 ⁇ m
- this condition is obtained by changing the film formation condition and the laser irradiation condition to produce a large number of grain-oriented electrical steel sheets having different warpage amounts as described above. evaluating the amount of warpage in the [Delta] S C and [Delta] S L, results of examining the relationship between core loss and magnetostriction of grain-oriented electrical steel sheet, the conditions for grain-oriented electrical steel sheet having both a low core loss and low magnetostriction are obtained It is what I have requested.
- the removal of the surface of the grain-oriented electrical steel sheet by pickling for measuring the amount of warp preferably removes all of the primary film, the tension insulating film, and the residual strained part by laser irradiation of the steel sheet base material. Accordingly, the surface of the grain-oriented electrical steel sheet is pickled so as to remove the range from the surface of the tension insulating coating to the depth position of 5 ⁇ m on the side of the steel plate base material from the interface between the steel plate base material and the primary coating. . It is preferable to remove to a depth position of 10 ⁇ m closer to the steel plate base material than the interface by pickling, and more preferable to remove to a depth position of 15 ⁇ m closer to the steel plate base material than the interface.
- the deepest position (upper limit) of the steel sheet base material removed by pickling may be less than 50 ⁇ m on the steel sheet base material side with respect to the interface. preferable.
- pickling of a grain-oriented electrical steel sheet can be performed by the following method, for example.
- the grain-oriented electrical steel sheet is immersed in a sodium hydroxide aqueous solution of NaOH: 10% by mass + H 2 O: 90% by mass at a high temperature for a predetermined time.
- a sulfuric acid aqueous solution of H 2 SO 4 10% by mass + H 2 O: 90% by mass at a high temperature for a predetermined time.
- HNO 3 10% by mass + H 2 O: 90% by mass.
- dry with a warm air blower for 1 minute What is necessary is just to control the surface removal amount of a grain-oriented electrical steel sheet by adjusting said immersion temperature and immersion time.
- the amount of warpage of the grain-oriented electrical steel sheet is obtained by taking a strip-shaped sample having a length of 300 mm in a direction parallel to the rolling direction and a length of 60 mm in a direction parallel to the sheet width direction from the grain-oriented electrical steel sheet. As shown in FIG. 2, the sample was pickled and placed vertically with 30 mm at one end in the longitudinal direction of the sample sandwiched between clamps, and the amount of displacement (warpage) at one end on the opposite side of the sample was measured.
- the grain-oriented electrical steel sheet By pickling only one side of the grain-oriented electrical steel sheet that has been laser-irradiated, the residual strain due to laser irradiation of the primary coating, the tension insulating coating, and the steel plate base material is removed (aspect a).
- the grain-oriented electrical steel sheet is bent by the film tension of the surface that has not been pickled. The amount of warpage in that case is proportional to the film tension.
- the coating is removed only on one side opposite to the laser-irradiated side of the grain-oriented electrical steel sheet (the above-mentioned mode b)
- the directional electromagnetic wave is generated by the coating tension and laser-applying stress of the surface not pickled.
- the steel plate is curved. The amount of warpage in that case is proportional to the sum of the film tension and the laser applied stress.
- the present inventors have found that the above upper limit of ⁇ S C (35000 ⁇ m) corresponds to the case where the tension insulating coating film weight 4.5 g / m 2, the lower limit value of ⁇ S C (15000 ⁇ m), the coating amount It was confirmed that it corresponds to the case where a 1.0 g / m 2 tensile insulating coating was applied. Further, the present inventors have found that the upper limit value of ⁇ S L (14000 ⁇ m) corresponds to a laser irradiation energy intensity at which magnetostriction is not excessive: 2.0 mJ / mm 2, and the lower limit value of ⁇ S L (900 ⁇ m) is an iron loss. It was confirmed that the laser irradiation energy density at which an improvement effect was obtained corresponds to 0.8 mJ / mm 2 .
- the coating amount of the coating is determined by the insulation resistance between the grain-oriented electrical steel sheets and the overall space factor.
- warpage [Delta] S C and [Delta] S L oriented electrical steel sheet is adjusted to the range of the .
- a tensile insulating coating having a coating amount in the range of 1.0 g / m 2 to 4.5 g / m 2 is applied and baked on both surfaces of the grain-oriented electrical steel sheet having the primary coating, respectively. It is confirmed that the laser beam should be irradiated with an irradiation energy density of 0.8 mJ / mm 2 to 2.0 mJ / mm 2 .
- the coating amount of the tension insulating coating is less than 1.0 g / m 2 , the insulation resistance between the grain-oriented electrical steel sheets is not sufficient when the iron core is produced by laminating.
- the coating amount of the tension insulating coating is more than 4.5 g / m 2 , the space factor decreases when the iron core is manufactured by stacking the directional electrical steel sheets. Since the energy loss of the transformer is deteriorated in both cases where the coating amount of the tension insulating coating is less than 1.0 g / m 2 and more than 4.5 g / m 2 , the coating amount of the tension insulating coating is the above-mentioned. The range.
- tensile_strength insulating film is mentioned later.
- the grain-oriented electrical steel sheet according to the present embodiment is excellent in both iron loss and magnetostriction as described above.
- the grain-oriented electrical steel sheet preferably has excellent space factor in addition to low iron loss and low magnetostriction.
- the thickness of the steel sheet base metal is reduced in order to reduce eddy current loss and improve iron loss. Iron loss is improved by reducing the thickness of the steel plate base material.
- the transformer iron core is constructed by laminating grain-oriented electrical steel sheets, but when the steel sheet base metal is made thin without changing the film thickness, the iron (steel) ) Volume ratio (this is called the space factor) decreases. This decrease in the space factor affects the effect of reducing energy loss. That is, in order to increase the space factor, it is preferable that the film of the grain-oriented electrical steel sheet is thin.
- the present inventors have made intensive studies, as a result, warpage: [Delta] S C and [Delta] S L after having controlled within the above range, the average thickness of the average film thickness d t and the primary coating of the tension insulating film in the unit ⁇ m by controlling the ratio of the d p R a (average film thickness d p of the average film thickness d t / 1 primary coating tension insulating coating) to 0.1 to 3.0, the effect of improving the iron loss and magnetostriction At the same time, it was found that the space factor can be further increased.
- the volume fraction of the steel sheet base material in the grain-oriented electrical steel sheet can be 97% or more even when the thickness of the steel sheet base material is reduced in order to reduce eddy current loss.
- the volume fraction of the steel plate base material in a grain-oriented electrical steel sheet is 98% or more, and it is further more preferable that it is 99% or more.
- the above effect is considered to be due to the difference in physical properties between the tensile insulating coating and the primary coating.
- the tension insulating coating is formed of phosphate, colloidal silica, or the like, and the primary coating is formed of forsterite Mg 2 SiO 4 or the like. Due to such a difference in material, there is a difference in physical properties between the tension insulating coating and the primary coating.
- the grain-oriented electrical steel sheet is excellent in vibration damping rate in addition to low iron loss and low magnetostriction.
- the vibration attenuation rate of the grain-oriented electrical steel sheet is large, it is possible to further reduce the vibration of electromagnetic application equipment such as a transformer.
- the inventors of the present invention controlled the ratio R (average film thickness d t of the tensile insulating film / average film thickness d p of the primary film) to be 0.1 or more and 1.5 or less.
- R average film thickness d t of the tensile insulating film / average film thickness d p of the primary film
- each of the grain-oriented electrical steel sheets according to the present embodiment is controlled by controlling the ratio R to be 0.1 or more and 3.0 or less. It is considered that the conditions are controlled so as to increase the vibration damping rate.
- the grain-oriented electrical steel sheet is excellent in heat removal in addition to low iron loss and low magnetostriction.
- the heat release property of the grain-oriented electrical steel sheet is large, it is possible to suppress the heat generation (joule heat) of the transformer and achieve high efficiency and downsizing of the electrical equipment.
- the inventors of the present invention controlled the ratio R (average film thickness d t of the tensile insulating film / average film thickness d p of the primary film) to be 0.1 or more and 1.0 or less. It has been found that the heat removal property of the grain-oriented electrical steel sheet can also be improved. This effect is also considered to be obtained due to the different physical properties of the tensile insulating coating and the primary coating.
- the space factor can be preferably improved.
- the vibration damping rate can be preferably improved by controlling the ratio R to be not less than 0.1 and not more than 1.5. Further, by controlling the ratio R to 0.1 or more and 1.0 or less, it is possible to preferably improve the heat removal performance in addition to the space factor and the vibration damping rate. By controlling the ratio R to 0.1 or more and 0.8 or less, more preferable space factor, vibration damping rate, and heat removal property can be obtained. By controlling the ratio R to be 0.1 or more and 0.3 or less, more preferable space factor, vibration damping rate, and heat removal property can be obtained.
- the ratio R between the average thickness d p of the average film thickness d t and the primary coating of the tension insulating film in order to limit the 0.1 to 3.0, the average thickness of the tension insulating film is more than 0.5 ⁇ m It is preferably 4.5 ⁇ m or less.
- the average film thickness of the tension insulating coating is more preferably 2.0 ⁇ m or less, 1.5 ⁇ m or less, 1.0 ⁇ m or less, or 0.8 ⁇ m or less.
- the total tension applied to the steel plate base material by the primary coating and the tension insulating coating is preferably 1 MPa or more and 10 MPa or less.
- the total tension applied to the steel plate base material by the primary coating and the tension insulating coating is preferably 1 MPa or more and 10 MPa or less.
- the measurement method of the average film thickness d p of the average film thickness d t and the primary coating of the tension insulating film can be used an averaging method by cross section observation.
- the averaging method by cross-sectional observation the cross section of the tension insulating coating and the primary coating is observed using a scanning electron microscope (SEM), and the film thickness at any 10 points is measured.
- SEM scanning electron microscope
- the thickness of the tension insulating coating at the measurement location is 2 ⁇ m.
- the grain-oriented electrical steel sheet is cut so that the cutting direction and the plate thickness direction are parallel to each other.
- the cut surface is polished with care so that the tension insulating coating and the primary coating do not peel off and fall off.
- the polished surface is etched with a preferable etching solution as necessary, and the cross section is observed.
- silicon steel material containing 1.0 mass% to 4.0 mass% of Si is subjected to hot rolling and cold rolling to produce a steel plate having a predetermined thickness.
- silicon steel material has a mass fraction of Si: 1.0% to 4.0%, C: more than 0% to 0.085%, acid-soluble Al: 0% to 0.065%, N: 0% to 0.012%, Mn: 0% to 1%, Cr: 0% to 0.3%, Cu: 0% to 0.4%, P: 0% to 0.
- decarburization annealing is performed on the steel sheet.
- the purpose of decarburization annealing is to improve the magnetic properties by removing C in the steel.
- Si in the steel is oxidized, and silica SiO 2 is formed on the surface of the steel plate.
- Silica reacts with magnesia MgO, which will be described later, to form forsterite Mg 2 SiO 4 constituting the primary coating. It is preferable to suppress the concentration of C to 30 ppm or less by decarburization annealing, and more preferably 20 ppm or less.
- the dew point of the decarburization annealing (oxidation degree PH 2 O / PH 2) is high, the oxidation reaction of C and Si is liable to proceed. Therefore, the higher the dew point, the more silica is formed, and the lower the dew point, the smaller the amount of silica formed. That is, it is possible to adjust the film thickness of the primary coating by adjusting the dew point during decarburization annealing. Specifically, reducing the dew point during decarburization annealing can reduce the thickness of the primary coating, and increasing the dew point during decarburization annealing can increase the thickness of the primary coating. Is possible.
- the dew point at the time of decarburization annealing is not particularly limited, for example, the range of the value of PH 2 O / PH 2 is 0.3 to 0.5.
- an annealing separator is applied to the steel sheet surface, and finish annealing is performed at a temperature of 1100 ° C. or higher. Finish annealing is aimed at secondary recrystallization, and in this process, a primary film containing forsterite is formed.
- the inhibitor forming elements are discharged out of the system. Therefore, in the grain-oriented electrical steel sheet finally obtained, the decrease in concentration is remarkable for N and S, and is 50 ppm or less.
- the concentration of N and S is preferably suppressed to 20 ppm or less, more preferably 10 ppm or less, still more preferably 9 ppm or less, and particularly preferably 6 ppm or less.
- a known method can be used, and in particular, a method of applying the annealing separator as a water slurry to a steel plate with a roll coater, a method of attaching powder to the steel plate by electrostatic coating, etc. preferable.
- the water slurry of the annealing separator contains a solid content mainly composed of magnesia.
- the film thickness of the primary film can be adjusted. Specifically, it is possible to reduce the film thickness of the primary coating by reducing the solid content in the water slurry of the annealing separator and the magnesia content in the solid content.
- additives are also used as the solid content of the annealing separator.
- Additives include those involved in the reaction between silica and magnesia, and those that move the silica on the surface of the steel sheet formed after decarburization annealing into the annealing separator to facilitate the removal of silica.
- alkali metal salts such as Li, Na, K, and Rb.
- the melting point of at least a part of the silica is lowered, and the silica exhibits fluidity.
- the silica having increased fluidity easily moves into the annealing separator (in the magnesia powder), and the silica transferred into the annealing separator is removed together with the removal of the annealing separator after the finish annealing. That is, the silica that has moved into the annealing separator does not participate in the formation of the primary film containing magnesium silicate, and as a result, the amount of Mg can be suppressed.
- the effect of the alkali metal salt becomes more remarkable.
- Silica that has become fluid due to the action of the alkali metal salt moves into the annealing separator, that is, into the magnesia powder, but when it contacts the surface of the magnesia particles, it reacts and loses fluidity.
- TiO 2 is less likely to react with silica than magnesia, so the presence of TiO 2 can move its surface without reacting with silica, and more silica can be contained in the annealing separator. Can be absorbed.
- it is possible to adjust the film thickness of the primary coating by adjusting the content of TiO 2 in the annealing separator.
- the content of TiO 2 in the annealing separator is determined by the balance with the content of the alkali metal salt and is not particularly limited.
- the content in the annealing separator is 1% by mass to 10% by mass.
- a tension insulating film is formed on the surface of the steel sheet.
- the tension insulating coating there is a coating formed by applying an aqueous coating solution containing phosphate and colloidal silica.
- the phosphate include phosphates such as Ca, Al, Mg, and Sr.
- the method for forming the tension insulating coating is not particularly limited, but it is possible to form the tension insulating coating by applying the above-mentioned aqueous coating solution to the surface of the steel sheet using a grooved coating roll or the like and baking it in the air. It is.
- the film thickness of the tension insulating coating can be adjusted by adjusting the interval and depth of the groove pitch of the grooved coating roll. Specifically, the film thickness of the tension insulating coating can be reduced by narrowing the groove pitch of the grooved coating roll and decreasing the depth.
- the baking temperature and baking time for forming the tension insulating coating are not particularly limited, and examples thereof include a baking temperature of 700 ° C. to 900 ° C. and a baking time of 10 seconds to 120 seconds.
- laser irradiation is performed on the grain-oriented electrical steel sheet.
- Laser irradiation may be performed in a continuous line shape in the sheet width direction at intervals in the rolling direction.
- a CO 2 laser, a YAG laser, a fiber laser, or the like can be used as the type of laser.
- the laser is preferably a continuous wave laser.
- stress is applied to the steel sheet by the impact reaction force of the laser, whereas in the continuous wave laser, the stress is applied to the steel sheet mainly by the thermal effect. Compared to this, it is considered that warpage is suppressed.
- the output of laser irradiation may be constant, or the output of laser irradiation may be changed between the center and the end in the longitudinal direction of the irradiation line.
- the laser output when the laser irradiation output is kept constant is not particularly limited, and examples include 0.8 mJ / mm 2 to 2.0 mJ / mm 2 .
- the laser irradiation output is not particularly limited.
- the laser irradiation output in the central portion in the irradiation line longitudinal direction is 1.2 mJ. / Mm 2 -2.0 mJ / mm 2 can be irradiated with laser, and the laser irradiation output at the end in the longitudinal direction of the irradiation line can be irradiated with 0.8 mJ / mm 2 -1.6 mJ / mm 2 It is.
- the end portion in the longitudinal direction of the irradiation line refers to a range represented by 1/3 when the length in the longitudinal direction of the irradiation line is l, and the central portion in the longitudinal direction of the irradiation line is otherwise Refers to the range.
- the direction at the center position where the laser beam is scanned at the time of laser irradiation may be a direction perpendicular to the rolling surface, or 1 ° to 10 ° from the direction perpendicular to the rolling surface.
- the range may be shifted.
- the desired [Delta] S C depending on the film thickness of [Delta] S L, the primary coating thickness and tension insulating film, it is possible to select as appropriate.
- a final finishing annealing is performed by applying an annealing separator mainly composed of MgO. And a grain-oriented electrical steel sheet having a primary coating was obtained.
- a coating treatment liquid composed of colloidal silica, aluminum phosphate, and magnesium phosphate was applied to the steel sheet and baked to form a tensile insulating coating. At this time, the coating amount of the tension insulating coating on the front and back surfaces of the steel sheet was changed by changing the coating amount of the coating treatment liquid.
- magnetic domain fragmentation treatment was performed on one surface of the steel sheet after the formation of the tension insulating coating, which was irradiated with continuous wave lasers having different irradiation energies.
- the laser was a CO 2 laser, and was irradiated at intervals of 5 mm in the direction perpendicular to the rolling direction under the conditions of irradiation line length in the rolling direction: 0.1 mm, output: 2 kW, and scanning speed: 100 to 600 m / s. .
- the iron loss W 17/50 and magnetostriction ⁇ 0-p of the grain oriented electrical steel sheets 1 to 7 were measured.
- the iron loss W 17/50 was measured using a single plate magnetic tester (SST).
- the magnetostriction lambda 0-p includes a material length L at the maximum excitation magnetic flux density was calculated from the material length L 0 Metropolitan in magnetic flux density 0.
- the average film thickness dt of the tension insulating coating and the average film thickness d p of the primary coating were averaged by cross-sectional observation. Specifically, using a scanning electron microscope, the cross section of the tension insulating coating and the primary coating is observed, the film thickness at any 10 points is measured, and the average value of the measured 10 points is used. It was.
- the space factor of the grain-oriented electrical steel sheet was measured by a method according to JIS C 2550: 2011.
- the coating amount of the tension insulation coating shown in Table 1 represents the coating amount per one side of the steel sheet.
- the ratio d t / d p between the average film thickness dt of the tensile insulating film and the average film thickness d p of the primary film is 0.1 to 3.0.
- the space factor is preferably improved.
- the vibration damping rate is preferably improved in addition to the space factor
- the ratio d t / d p is It was found that in the case of 0.1 to 1.0, the heat removal property is preferably improved in addition to the space factor and the vibration damping rate.
- no. No. 3 sample ratio d t / d p is 0.63) No.
- the vibration damping rate was improved by 20% and the heat removal rate in the stacking direction was improved by 15%.
- a grain-oriented electrical steel sheet excellent in both iron loss and magnetostriction can be provided.
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Abstract
Description
本願は、2014年5月9日に、日本に出願された特願2014-97685号に基づき優先権を主張し、その内容をここに援用する。
変圧器は、据え付けられてから廃棄されるまで長期間にわたって連続的に励磁され、エネルギー損失を発生し続けることから、これらの特性うち、特に鉄損が低いことが求められている。
そこで、被膜が形成された方向性電磁鋼板にレーザ照射して磁区制御を行う際に、レーザ照射条件及び被膜張力を調整することにより磁歪を低減して、低鉄損と低磁歪とを両立させるための技術が、特許文献1~4に開示されている。
特許文献1には、1次被膜とその後に付与する2次被膜による合計の鋼板への張力を1~8MPaとし、鋼板の単位面積当たりの入熱量を1~2mJ/mm2となるようにパルスレーザ照射し、あるいは、前記張力を14MPa以上とし、前記入熱量を1.5~3mJ/mm2とすることが開示されている。
本発明は、上記の事情に鑑みてなされたものであり、低鉄損と低磁歪とを両立する方向性電磁鋼板を提供することを目的とする。
例えば、方向性電磁鋼板に付与している被膜(張力絶縁被膜及び1次被膜(グラス被膜))によって鋼板母材には応力が加わるが、磁区制御のためのレーザ照射によっても鋼板母材に応力が加わる。
本発明者らは、これらの応力分布の影響度合いによって、上記の鉄損及び磁歪をバランスよく最小化する被膜張力及びレーザ付与応力の範囲が存在することを見出した。
そして、上記応力を方向性電磁鋼板の反り量の変化によって評価して、磁歪が最適になる範囲を見出した。
(1)本発明の一態様に係る方向性電磁鋼板は、鋼板母材と、前記鋼板母材の表面に形成された1次被膜と、前記1次被膜の表面に形成された張力絶縁被膜とを有し、前記張力絶縁被膜の上からレーザを照射することにより磁区制御がなされている。前記方向性電磁鋼板の圧延方向と平行な方向の長さが300mmかつ板幅方向と平行な方向の長さが60mmである短冊状のサンプルを前記方向性電磁鋼板から採取し、前記サンプルの少なくとも片面を酸洗することにより、前記張力絶縁被膜の表面から、前記鋼板母材と前記1次被膜との界面よりも前記鋼板母材側に5μmの深さ位置までの範囲を除去した後に前記サンプルの反り量を測定したとき、前記反り量が下記の式A及び式Bを満たす。
15000μm≦SA-SC≦35000μm ・・・(式A)
900μm≦SB+SC≦14000μm ・・・(式B)
ここで、SA、SB、SCは以下を示す。
SA;レーザ照射した側の片面のみを酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
SB;レーザ照射した側と反対側の片面のみを酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
SC;両面を酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
ただし、SAとSBの測定の際には酸洗した面と同一方向への反りを正の値とし、SCはSAと同じ方向への反りを正の値と定義する。
両方の表面に1次被膜(グラス被膜)と張力絶縁被膜とが形成された方向性電磁鋼板において、一方の表面にレーザ照射による磁区細分化処理が施された方向性電磁鋼板は、被膜張力による応力とレーザ照射による応力とが付加されている。
磁歪が電磁鋼板に加えられる応力により大きく影響されることはよく知られている。上述の2つの応力の大きさにより、磁歪に対する影響度合いが変化する。
本発明者らは、1次被膜と張力絶縁被膜とからなる被膜張力の磁歪に対する影響度合いと、レーザ照射による応力の磁歪に対する影響度合いとについてさらに詳細に検討した。
その結果、被膜張力による応力及びレーザ照射による応力を方向性電磁鋼板の反り量で評価し、被膜張力による応力に基づく反り量の変化と、被膜張力による応力及びレーザ照射による応力に基づく反り量の変化とを調整することにより、磁歪が最適になる範囲が存在することを見出した。
Siを3.2質量%含有し、板厚0.23mmに圧延された冷延鋼板に対して、露点を変化させて脱炭焼鈍及び一次再結晶焼鈍を施した。その後、MgOを主成分とする焼鈍分離剤を鋼板表面に塗布した状態で仕上焼鈍を施して、様々な厚みの1次被膜(グラス被膜)を有する方向性電磁鋼板素材を得た。
ついで、得られた方向性電磁鋼板素材から多数のサンプルを切り出し、コロイダルシリカとリン酸アルミニウムとを含有するコーティング処理液を塗布した。コーティング処理液の塗布量は、サンプルごとに変化させた。コーティング処理液を塗布したサンプルを800℃の温度で焼付けて、様々な厚みの張力絶縁被膜(2次被膜)を形成した。その後、それぞれのサンプルの片面に、異なる照射エネルギー(入熱量)の連続波レーザを照射する磁区細分化処理を施した。
これによって、被膜の成膜条件とレーザ照射条件とが異なる多数の方向性電磁鋼板を得た。
なお、鉄損W17/50は、励磁磁束密度1.7Tにおける50Hzでの鉄損であり、単板磁気試験器(SST)を用いて測定した。
また、磁歪λ0-pは、例えば50Hzで励磁したときの最大励磁磁束密度における材料長さLと、磁束密度0における材料長さL0とを用いて、下式(1)により算出した。
λ0-p=(L-L0)/L0・・・(1)
a.サンプルのレーザ照射した側の片面のみを酸洗
b.サンプルのレーザ照射した側と反対側の片面のみを酸洗
c.サンプルの両面を酸洗
酸洗後の反り量は、図2に示すように、サンプルの長手方向の一端の30mmをクランプに挟んだ状態で垂直に載置し、反対側の一端の変位量(反り量)を測定して求めた。測定に当たっては、aの態様及びbの態様の測定の際には酸洗した面と同一方向への反りを正の値とし、cの態様の測定の際にはaの態様と同じ方向への反りを正の値とした。
レーザ照射した側の片面のみを酸洗した時の方向性電磁鋼板の反り量(μm);SA、
レーザ照射した側と反対側の片面のみを酸洗した時の方向性電磁鋼板の反り量(μm);SB、
両面を酸洗した時の方向性電磁鋼板の反り量(μm);SC
とし、
ΔSC=SA-SC、
ΔSL=SB+SC
として、
各サンプルのΔSC及びΔSLに対する鉄損と磁歪との関係を調べた。
図1より、ΔSCとΔSLとのいずれもが、
ΔSC:15000~35000μm、
ΔSL:900~14000μm
の範囲にあるときに、低鉄損と低磁歪とを両立する結果が得られた。
本実施形態では、製造過程の仕上焼鈍において鋼板母材の両面に形成された1次被膜(代表的にはフォルステライト被膜)とその上に塗布・焼き付けられた張力絶縁被膜を有し、さらに、片面にレーザを照射して磁区制御がなされた方向性電磁鋼板を対象とする。
なお、日本国特開昭54-43115号公報に開示されているように、鏡面状態の表面を有する方向性電磁鋼板上に、張力絶縁被膜を形成する場合でも、本実施形態の思想を損ねるものではない。
酸洗により、上記界面よりも鋼板母材側に10μmの深さ位置まで除去することが好ましく、上記界面よりも鋼板母材側に15μmの深さ位置まで除去することがさらに好ましい。
ただし、酸洗により、上記界面よりも鋼板母材側に50μmの深さ位置まで除去すると、方向性電磁鋼板の板厚が薄くなりすぎ、反り量等の測定において十分な測定精度を確保できなくなる。そのため、方向性電磁鋼板の表面の酸洗を行う際には、酸洗により除去される鋼板母材の最深位置(上限値)を、上記界面よりも鋼板母材側に50μm未満とすることが好ましい。
また、方向性電磁鋼板のレーザ照射された側とは反対の片面のみ被膜を除去する(上記bの態様)と、酸洗を行わなかった面の有する被膜張力及びレーザ付与応力によって、方向性電磁鋼板は湾曲する。その場合の反り量は、被膜張力とレーザ付与応力との合計に比例する。
また、本発明者らは、ΔSLの上限値(14000μm)は、磁歪が過大とならないレーザ照射エネルギー強度:2.0mJ/mm2に対応し、ΔSLの下限値(900μm)は、鉄損向上効果が得られるレーザ照射エネルギー密度:0.8mJ/mm2に対応していることを確認した。
なお、張力絶縁被膜の製造方法については後述する。
なお、方向性電磁鋼板中の鋼板母材の体積分率が98%以上であることが好ましく、99%以上であることがさらに好ましい。
上記の比率Rを0.1以上0.8以下に制御することにより、より好ましい占積率、振動減衰率及び抜熱性を得ることができる。上記の比率Rを0.1以上0.3以下に制御することにより、さらに好ましい占積率、振動減衰率及び抜熱性を得ることができる。
張力絶縁被膜の平均膜厚は、2.0μm以下、1.5μm以下、1.0μm以下、0.8μm以下であることがより好ましい。
張力絶縁被膜の平均膜厚dt及び1次被膜の平均膜厚dpの測定方法としては、断面観察による平均化法以外に、カロテスト(登録商標)法等を用いることができる。
なお、被膜中に含まれる空孔は、膜厚測定の算出から除外する。例えば、張力絶縁被膜の表面から1次被膜との界面までの厚さが3μmであるが、その中に1μmの空孔が含まれる場合には、その測定箇所での張力絶縁被膜の膜厚は2μmとする。
また、上記の断面観察は、次の手順にて行うことが好ましい。切断方向と板厚方向とが平行となるように方向性電磁鋼板を切断する。この切断面を張力絶縁被膜および1次被膜が剥離して脱落しないように注意して研磨する。この研磨面を必要に応じて好ましいエッチング液にてエッチングして上記の断面観察を行う。
Siを1.0質量%~4.0質量%含有するけい素鋼素材を、熱間圧延及び冷間圧延を経て、所定の板厚を有する鋼板を製造する。なお、けい素鋼素材は、代表的な化学成分として、質量分率で、Si:1.0%~4.0%、C:0%超~0.085%、酸可溶性Al:0%~0.065%、N:0%~0.012%、Mn:0%~1%、Cr:0%~0.3%、Cu:0%~0.4%、P:0%~0.5%、Sn:0%~0.3%、Sb:0%~0.3%、Ni:0%~1%、S:0%~0.015%、Se:0%~0.015%、などを含有し、残部がFe及び不純物からなってもよい。
脱炭焼鈍により、Cの濃度を30ppm以下に抑制することが好ましく、より好ましくは20ppm以下である。
脱炭焼鈍の露点(酸化度PH2O/PH2)が高くなると、C及びSiの酸化反応が進みやすくなる。したがって、露点が高いほど多くのシリカが形成され、露点を低くすると形成されるシリカ量が少なくなる。
つまり、脱炭焼鈍時の露点を調整することにより、1次被膜の膜厚を調整することが可能である。具体的には、脱炭焼鈍時の露点を下げることにより、1次被膜の膜厚を小さくすることが、脱炭焼鈍時の露点を上げることにより、1次被膜の膜厚を大きくすることが、可能である。
脱炭焼鈍時の露点は特に限定されないが、例えば、PH2O/PH2の値の範囲として、0.3~0.5が挙げられる。
焼鈍分離剤の塗布方法は、公知の方法を用いることができ、特に、焼鈍分離剤を水スラリーとしてロールコーターなどで鋼板に塗布する方法、静電塗布にて鋼板に紛体を付着させる方法などが好ましい。
焼鈍分離剤の水スラリーは、マグネシアを主成分とする固形分を含んでおり、水スラリーにおける固形分の含有量及び固形分中のマグネシアの含有量を調整することにより、1次被膜の膜厚を調整することができる。具体的には、焼鈍分離剤の水スラリーにおける固形分の含有量及び固形分中のマグネシアの含有量を少なくすることにより、1次被膜の膜厚を小さくすることが可能である。
焼鈍分離剤にアルカリ金属塩を添加することにより、仕上げ焼鈍の過程で、アルカリ金属塩が脱炭焼鈍で形成された鋼板表面のシリカに作用する。これにより、少なくとも一部のシリカの融点が下がり、シリカが流動性を示すようになる。流動性が高くなったシリカは、焼鈍分離剤中(マグネシア粉末中)に移動しやすくなり、焼鈍分離剤中に移動したシリカは仕上げ焼鈍後に焼鈍分離剤の除去と共に除去される。すなわち、焼鈍分離剤中へ移動したシリカは、マグネシウムケイ酸塩を含む1次被膜の形成には関与せず、その結果としてMg量が抑制できる。
アルカリ金属塩の作用によって流動性を示すようになったシリカは、焼鈍分離剤中、すなわち、マグネシア粉末中に移動するが、マグネシア粒子の表面に接触すると、反応して流動性を失ってしまう。一方、TiO2は、マグネシアに比べてシリカと反応し難いので、TiO2が存在することにより、シリカが反応せずにその表面を移動することができ、より多くのシリカを焼鈍分離剤中に吸収させることができる。
上述の理由から、焼鈍分離剤中のTiO2の含有量を調整することにより、1次被膜の膜厚を調整することが可能である。具体的には、焼鈍分離剤中のTiO2の含有量を少なくすることにより、1次被膜の膜厚を小さくすることが可能である。
焼鈍分離剤中のTiO2の含有量はアルカリ金属塩の含有量とのバランスにより決められ、特に限定されないが、例えば、焼鈍分離剤中における含有量は1質量%~10質量%である。
ここで、溝付き塗布ロールの溝ピッチの間隔及び深さを調整することにより、張力絶縁被膜の膜厚を調整することができる。具体的には、溝付き塗布ロールの溝ピッチを狭く、かつ、深さを浅くすることにより、張力絶縁被膜の膜厚を小さくすることができる。
張力絶縁被膜を形成する際の焼付け温度及び焼付け時間は特に限定されないが、例えば、焼付け温度は700℃~900℃、焼付け時間は10秒~120秒が挙げられる。
レーザ照射は、圧延方向に間隔を置いて、板幅方向に連続線状に照射すればよい。レーザの種類は、CO2レーザ、YAGレーザ又はファイバーレーザ等を用いることができる。
レーザ照射による鋼板反りへの影響を抑えるには、レーザは連続波レーザとすることが好ましい。パルスレーザでは、レーザによる衝撃反力によって鋼板に応力が付与されるのに対し、連続波レーザでは、主に熱効果によって鋼板に応力が付与されるため、応力の分布状態が異なり、パルスレーザに比べ反りが抑制されるものと考えられる。
レーザ照射の出力を一定にする場合のレーザ出力は特に限定されないが、例えば、0.8mJ/mm2~2.0mJ/mm2が挙げられる。
照射線長手方向の中心部と端部とでレーザ照射の出力を変化させる場合において、レーザ照射の出力は特に限定されないが、例えば、照射線長手方向の中心部におけるレーザ照射の出力を1.2mJ/mm2~2.0mJ/mm2としてレーザを照射し、照射線長手方向の端部におけるレーザ照射の出力を0.8mJ/mm2~1.6mJ/mm2としてレーザを照射することが可能である。
ここで、照射線長手方向の端部とは、照射線の長手方向の長さをlとした場合に、l/3で表される範囲を指し、照射線長手方向の中心部とはそれ以外の範囲を指す。
鉄損W17/50は、単板磁気試験器(SST)を用いて測定した。
磁歪λ0-pは、最大励磁磁束密度における材料長さLと、磁束密度0における材料長さL0とから算出した。
また、方向性電磁鋼板の占積率は、JIS C 2550:2011に準ずる方法で測定した。
なお、表1に示す張力絶縁被膜の被膜量は、鋼板片面当たりの被膜量を表している。
Claims (6)
- 鋼板母材と、前記鋼板母材の表面に形成された1次被膜と、前記1次被膜の表面に形成された張力絶縁被膜とを有し、前記張力絶縁被膜の上からレーザを照射することにより磁区制御がなされた方向性電磁鋼板であって、
前記方向性電磁鋼板の圧延方向と平行な方向の長さが300mmかつ板幅方向と平行な方向の長さが60mmである短冊状のサンプルを前記方向性電磁鋼板から採取し、前記サンプルの少なくとも片面を酸洗することにより、前記張力絶縁被膜の表面から、前記鋼板母材と前記1次被膜との界面よりも前記鋼板母材側に5μmの深さ位置までの範囲を除去した後に前記サンプルの反り量を測定したとき、
前記反り量が下記の式A及び式Bを満たす
ことを特徴とする方向性電磁鋼板。
15000μm≦SA-SC≦35000μm ・・・(式A)
900μm≦SB+SC≦14000μm ・・・(式B)
ここで、SA、SB、SCは以下を示す。
SA;レーザ照射した側の片面のみを酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
SB;レーザ照射した側と反対側の片面のみを酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
SC;両面を酸洗した時の前記方向性電磁鋼板の単位μmでの反り量
ただし、SAとSBの測定の際には酸洗した面と同一方向への反りを正の値とし、SCはSAと同じ方向への反りを正の値と定義する。 - 前記張力絶縁被膜の単位μmでの平均膜厚dtを前記1次被膜の単位μmでの平均膜厚dpで除した値dt/dpが0.1以上3.0以下である
ことを特徴とする請求項1に記載の方向性電磁鋼板。 - 前記張力絶縁被膜の単位μmでの平均膜厚dtを前記1次被膜の単位μmでの平均膜厚dpで除した値dt/dpが0.1以上1.5以下である
ことを特徴とする請求項1に記載の方向性電磁鋼板。 - 前記張力絶縁被膜の単位μmでの平均膜厚dtを前記1次被膜の単位μmでの平均膜厚dpで除した値dt/dpが0.1以上1.0以下である
ことを特徴とする請求項1に記載の方向性電磁鋼板。 - 前記張力絶縁被膜の平均膜厚が0.5μm以上4.5μm以下である
ことを特徴とする請求項1から4の何れか1項に記載の方向性電磁鋼板。 - 前記1次被膜及び前記張力絶縁被膜によって前記鋼板母材に与えられる合計の張力が1MPa以上10MPa以下である
ことを特徴とする請求項1から5の何れか1項に記載の方向性電磁鋼板。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107326379A (zh) * | 2017-06-06 | 2017-11-07 | 唐山钢铁集团有限责任公司 | 推拉酸洗机组酸洗电工钢的方法 |
EP3395963A4 (en) * | 2015-12-24 | 2018-12-12 | Posco | Grain-oriented electrical steel sheet and method for manufacturing same |
WO2020138373A1 (ja) * | 2018-12-27 | 2020-07-02 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
WO2020138374A1 (ja) * | 2018-12-27 | 2020-07-02 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101762339B1 (ko) * | 2015-12-22 | 2017-07-27 | 주식회사 포스코 | 방향성 전기강판 및 방향성 전기강판의 제조방법 |
KR102091631B1 (ko) * | 2018-08-28 | 2020-03-20 | 주식회사 포스코 | 방향성 전기강판 및 그 자구미세화 방법 |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08222423A (ja) * | 1995-02-13 | 1996-08-30 | Kawasaki Steel Corp | 鉄損の低い方向性けい素鋼板およびその製造方法 |
JP2002356750A (ja) * | 2000-05-12 | 2002-12-13 | Nippon Steel Corp | 低鉄損、低騒音の方向性電磁鋼板及びその製造方法 |
JP2005317683A (ja) * | 2004-04-27 | 2005-11-10 | Nippon Steel Corp | 3相積み鉄心用の方向性電磁鋼板 |
JP2011246770A (ja) * | 2010-05-27 | 2011-12-08 | Nippon Steel Corp | 方向性電磁鋼板及び張力絶縁膜被覆方向性電磁鋼板 |
WO2012017670A1 (ja) * | 2010-08-06 | 2012-02-09 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
JP2012031519A (ja) * | 2010-06-30 | 2012-02-16 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
JP2012036447A (ja) * | 2010-08-06 | 2012-02-23 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
WO2013099160A1 (ja) * | 2011-12-26 | 2013-07-04 | Jfeスチール株式会社 | 方向性電磁鋼板 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63286521A (ja) | 1987-05-20 | 1988-11-24 | Nippon Steel Corp | 方向性珪素鋼板の焼鈍分離剤塗布方法 |
JP2671088B2 (ja) | 1992-11-12 | 1997-10-29 | 新日本製鐵株式会社 | 磁気特性が優れ、鉄心加工性が著しく優れた高磁束密度方向性電磁鋼板及びその製造法 |
KR100442099B1 (ko) * | 2000-05-12 | 2004-07-30 | 신닛뽄세이테쯔 카부시키카이샤 | 저철손 및 저소음 방향성 전기 강판 및 그의 제조 방법 |
JP2002220642A (ja) * | 2001-01-29 | 2002-08-09 | Kawasaki Steel Corp | 鉄損の低い方向性電磁鋼板およびその製造方法 |
TWI305548B (en) * | 2005-05-09 | 2009-01-21 | Nippon Steel Corp | Low core loss grain-oriented electrical steel sheet and method for producing the same |
JP4846429B2 (ja) | 2005-05-09 | 2011-12-28 | 新日本製鐵株式会社 | 低鉄損方向性電磁鋼板およびその製造方法 |
KR101234452B1 (ko) * | 2008-02-19 | 2013-02-18 | 신닛테츠스미킨 카부시키카이샤 | 저철손 일방향성 전자기 강판 및 그 제조 방법 |
RU2503729C1 (ru) | 2010-06-25 | 2014-01-10 | Ниппон Стил Энд Сумитомо Метал Корпорейшн | Способ изготовления листа из электротехнической стали с ориентированной зеренной структурой |
JP5927754B2 (ja) | 2010-06-29 | 2016-06-01 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
JP6084351B2 (ja) * | 2010-06-30 | 2017-02-22 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
JP5594252B2 (ja) | 2010-08-05 | 2014-09-24 | Jfeスチール株式会社 | 方向性電磁鋼板の製造方法 |
-
2015
- 2015-05-08 WO PCT/JP2015/063357 patent/WO2015170755A1/ja active Application Filing
- 2015-05-08 CN CN201580023695.8A patent/CN106460111B/zh active Active
- 2015-05-08 PL PL15788697T patent/PL3141626T3/pl unknown
- 2015-05-08 RU RU2016144288A patent/RU2665666C2/ru active
- 2015-05-08 EP EP15788697.9A patent/EP3141626B1/en active Active
- 2015-05-08 US US15/308,781 patent/US10610964B2/en active Active
- 2015-05-08 KR KR1020167031158A patent/KR101907768B1/ko active IP Right Grant
- 2015-05-08 BR BR112016025466-0A patent/BR112016025466B1/pt active IP Right Grant
- 2015-05-08 JP JP2016517949A patent/JP6315084B2/ja active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08222423A (ja) * | 1995-02-13 | 1996-08-30 | Kawasaki Steel Corp | 鉄損の低い方向性けい素鋼板およびその製造方法 |
JP2002356750A (ja) * | 2000-05-12 | 2002-12-13 | Nippon Steel Corp | 低鉄損、低騒音の方向性電磁鋼板及びその製造方法 |
JP2005317683A (ja) * | 2004-04-27 | 2005-11-10 | Nippon Steel Corp | 3相積み鉄心用の方向性電磁鋼板 |
JP2011246770A (ja) * | 2010-05-27 | 2011-12-08 | Nippon Steel Corp | 方向性電磁鋼板及び張力絶縁膜被覆方向性電磁鋼板 |
JP2012031519A (ja) * | 2010-06-30 | 2012-02-16 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
WO2012017670A1 (ja) * | 2010-08-06 | 2012-02-09 | Jfeスチール株式会社 | 方向性電磁鋼板およびその製造方法 |
JP2012036447A (ja) * | 2010-08-06 | 2012-02-23 | Jfe Steel Corp | 方向性電磁鋼板およびその製造方法 |
WO2013099160A1 (ja) * | 2011-12-26 | 2013-07-04 | Jfeスチール株式会社 | 方向性電磁鋼板 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3141626A4 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3395963A4 (en) * | 2015-12-24 | 2018-12-12 | Posco | Grain-oriented electrical steel sheet and method for manufacturing same |
CN107326379A (zh) * | 2017-06-06 | 2017-11-07 | 唐山钢铁集团有限责任公司 | 推拉酸洗机组酸洗电工钢的方法 |
WO2020138373A1 (ja) * | 2018-12-27 | 2020-07-02 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
WO2020138374A1 (ja) * | 2018-12-27 | 2020-07-02 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
JP2020105595A (ja) * | 2018-12-27 | 2020-07-09 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
JP2020105596A (ja) * | 2018-12-27 | 2020-07-09 | Jfeスチール株式会社 | 方向性電磁鋼板用焼鈍分離剤および方向性電磁鋼板の製造方法 |
US11926888B2 (en) | 2018-12-27 | 2024-03-12 | Jfe Steel Corporation | Annealing separator for grain-oriented electrical steel sheet and method of producing grain-oriented electrical steel sheet |
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