WO2022250156A1 - 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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- WO2022250156A1 WO2022250156A1 PCT/JP2022/021829 JP2022021829W WO2022250156A1 WO 2022250156 A1 WO2022250156 A1 WO 2022250156A1 JP 2022021829 W JP2022021829 W JP 2022021829W WO 2022250156 A1 WO2022250156 A1 WO 2022250156A1
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- steel sheet
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- rolled steel
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 122
- 239000010959 steel Substances 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 136
- 238000005261 decarburization Methods 0.000 claims abstract description 41
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000005554 pickling Methods 0.000 claims abstract description 28
- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 claims description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 150000002500 ions Chemical class 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 46
- 238000000576 coating method Methods 0.000 abstract description 46
- 238000000034 method Methods 0.000 abstract description 34
- 238000005098 hot rolling Methods 0.000 abstract description 9
- 238000005097 cold rolling Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 57
- 239000000243 solution Substances 0.000 description 21
- 239000003112 inhibitor Substances 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 14
- 229910052839 forsterite Inorganic materials 0.000 description 12
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052711 selenium Inorganic materials 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
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- 229910052782 aluminium Inorganic materials 0.000 description 4
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- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
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- 230000005764 inhibitory process Effects 0.000 description 3
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- 239000002244 precipitate Substances 0.000 description 3
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- 229910000976 Electrical steel Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 230000005415 magnetization Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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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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- 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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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Definitions
- the present invention relates to a method for manufacturing a grain-oriented electrical steel sheet.
- Electrical steel sheet is a material widely used as iron cores for transformers and motors. Electrical steel sheets are broadly classified into grain-oriented electrical steel sheets and non-oriented electrical steel sheets. A grain-oriented electrical steel sheet has a texture in which the ⁇ 001> orientation, which is the axis of easy magnetization of iron, is highly aligned in the rolling direction of the steel sheet. It is characterized by
- Such a texture is formed by causing secondary recrystallization in the final annealing.
- secondary recrystallization refers to a phenomenon in which crystal grains of ⁇ 110 ⁇ 001> orientation, so-called Goss orientation, preferentially grow into large grains by utilizing grain boundary energy.
- a typical technique for causing the above secondary recrystallization is a technique that uses precipitates called inhibitors.
- Techniques using inhibitors include, for example, a method using AlN and MnS described in Patent Document 1, a method using MnS and MnSe described in Patent Document 2, and the like, all of which have been industrially put into practical use.
- the above method using an inhibitor has been widely used in the production of grain-oriented electrical steel sheets because it is possible to stably develop secondary recrystallized grains.
- Patent Document 3 a method of manufacturing grain-oriented electrical steel sheets without using an inhibitor (inhibitor-less method) has been proposed (for example, Patent Document 3).
- the inhibitorless method is a technology that uses highly purified steel and controls the texture to develop secondary recrystallization. Specifically, the dependence of the grain boundary energy on the grain boundary during the primary recrystallization on the misorientation angle of the grain boundary is made apparent, so that the grains having the Goss orientation can be secondary recrystallized without using an inhibitor. It is possible to Such an effect is called a texture inhibition effect.
- the inhibitorless method there is no need to finely disperse the inhibitor in the steel, so there is no need to heat the slab at a high temperature, which is essential when using an inhibitor. Therefore, the inhibitorless method has a great advantage not only in terms of manufacturing cost but also in terms of maintenance of manufacturing equipment.
- an annealing separator containing MgO is applied to the surface of the cold-rolled steel sheet after decarburization annealing, and then finish annealing is performed.
- a forsterite coating is formed on the surface of the steel sheet. If the forsterite coating is peeled off when manufacturing an iron core for a transformer using a grain-oriented electrical steel sheet, insulation cannot be ensured, so the grain-oriented electrical steel sheet is required to have excellent coating adhesion.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a grain-oriented electrical steel sheet that can obtain a grain-oriented electrical steel sheet with excellent film adhesion.
- % of acid concentration and Fe ion concentration represents “% by mass”. Also, “%” of the CO concentration in the atmosphere represents “% by volume”.
- Example 1 A steel slab for grain-oriented electrical steel sheets containing C: 0.048%, Si: 3.44%, and Mn: 0.10% by mass is heated to a temperature of 1400 ° C. and hot rolled to obtain a plate. A hot-rolled steel sheet having a thickness of 3.0 mm was used. The hot-rolled steel sheet was subjected to hot-rolled steel annealing at 950° C. for 40 seconds, and then pickled to remove scales on the surface of the steel sheet.
- the pickled hot-rolled steel sheet is first cold-rolled to a thickness of 0.7 mm, subjected to intermediate annealing at 1050 ° C. for 100 seconds, and then cold-rolled for the second time to obtain a sheet.
- a cold-rolled steel sheet having a thickness of 0.23 mm was used.
- the cold-rolled steel sheets were pickled in hydrochloric acid solutions containing Fe ions at various concentrations at a temperature of 50° C. and an acid concentration of 5%. The acid concentration and Fe ion concentration were measured using an ultrasonic densitometer manufactured by Fuji Kogyo Co., Ltd.
- the Fe ions in the hydrochloric acid solution were added as iron (III) chloride hexahydrate. Further, when the hydrochloric acid solution is used for pickling, the Fe ion concentration increases with the elution of iron from the cold-rolled steel sheet. Therefore, when pickling, the Fe ion concentration of the hydrochloric acid solution was monitored using the ultrasonic concentration measuring instrument, and the Fe ion concentration was kept constant by adding an aqueous hydrochloric acid solution as necessary.
- decarburization annealing was performed at 850°C for 90 seconds, 50% H 2 +50% N 2 , and a dew point of 60°C. At this time, the CO concentration in the annealing furnace was controlled to 2%.
- the surface of the steel sheet was coated with an annealing separation agent mainly composed of MgO, and subjected to final annealing at 1180° C. for 15 hours in an H 2 atmosphere.
- an annealing separation agent mainly composed of MgO was applied, and the coating was baked at 850° C. for 50 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the coating adhesion of the obtained grain-oriented electrical steel sheets was evaluated.
- the coating adhesion was evaluated by winding grain-oriented electrical steel sheets around cylinders having various diameters and determining the minimum diameter at which the coating did not peel off. The smaller the minimum diameter, the better the film adhesion.
- Fig. 1 shows the relationship between the Fe ion concentration of the solution used for pickling and the film adhesion. From this result, it can be seen that good film adhesion is exhibited when the Fe ion concentration is 2% or more and 15% or less.
- the pickled hot-rolled steel sheet is first cold-rolled to a thickness of 0.6 mm, subjected to intermediate annealing at 1100 ° C. for 100 seconds, and then cold-rolled for the second time to obtain a sheet.
- a cold-rolled steel sheet having a thickness of 0.23 mm was used.
- the cold-rolled steel sheets were pickled in hydrochloric acid solutions having various acid concentrations at a temperature of 40° C. and an Fe ion concentration of 6%. Other conditions for the pickling were the same as in Experiment 1 above.
- decarburization annealing was performed at 850°C for 180 seconds, 50% H 2 +50% N 2 , and a dew point of 62°C. At this time, the CO concentration in the annealing furnace was controlled to 1.5%.
- the surface of the steel sheet was coated with an annealing separation agent mainly composed of MgO, and subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- an annealing separation agent mainly composed of MgO was applied, and the coating was baked at 850° C. for 20 seconds and the steel sheet was flattened. Flattening annealing was applied.
- FIG. 2 shows the relationship between acid concentration and film adhesion. From this result, it can be seen that good film adhesion is exhibited when the acid concentration is 1.0% or more and 20% or less.
- the pickled hot-rolled steel sheet is first cold-rolled to a thickness of 1.6 mm, subjected to intermediate annealing at 1025° C. for 150 seconds, and then cold-rolled for the second time to obtain a sheet.
- a cold-rolled steel sheet having a thickness of 0.23 mm was used.
- the cold-rolled steel sheet was pickled in a hydrochloric acid solution having a temperature of 60° C., an acid concentration of 5%, and an Fe ion concentration of 13%. Other conditions for the pickling were the same as in Experiment 1 above.
- decarburization annealing was performed at 835°C x 180 seconds, 50% H 2 +50% N 2 , dew point 62°C. At this time, the CO concentration in the annealing furnace was variously changed.
- the surface of the steel sheet was coated with an annealing separation agent mainly composed of MgO, and subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- an annealing separation agent mainly composed of MgO was applied, and the coating was baked at 850° C. for 20 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the film adhesion of the obtained grain-oriented electrical steel sheets was evaluated in the same manner as in Experiments 1 and 2 above.
- the amount of C in the steel of the obtained grain-oriented electrical steel sheets was measured.
- the measurement of the amount of C in the steel was carried out after the film present on the surface of the grain-oriented electrical steel sheet was removed by pickling with hydrochloric acid of 5% concentration at 90°C.
- Fig. 3 shows the relationship between the in-furnace CO concentration during decarburization annealing, the film adhesion, and the amount of C in the steel.
- the amount of C in the steel of a grain-oriented electrical steel sheet exceeds 35 ppm, the iron loss characteristics deteriorate due to magnetic aging, so 35 ppm or less is considered acceptable. From this result, it can be seen that if the CO concentration in the furnace during decarburization annealing is 6% or less, the film adhesion is good and the C content in the steel falls within the acceptable range of 35 ppm or less.
- the forsterite coating is formed by reaction between an internal oxide layer mainly composed of silica developed under appropriate conditions during decarburization annealing and MgO contained in the annealing separator during final annealing.
- the surface of the steel sheet was uniformly cleaned before decarburization annealing, promoting the development of an internal oxide layer during decarburization annealing.
- the Fe ions functioned as a catalyst to promote the cleaning of the surface of the steel sheet by the acid. That is, when the Fe ions are small, the reactivity between the steel sheet surface and the acid in the acid solution is poor, and the surface cleaning is considered to be insufficient. Moreover, when the Fe ions are too large, the pickling effect is reduced, and it is considered that the cleaning is also insufficient.
- the decarburization reaction was suppressed when the CO concentration in the furnace was high. That is, C in steel reacts with water vapor in a moist atmosphere and is released into the atmosphere as CO and CO2 . If the CO concentration in the furnace is high, the reaction is suppressed, and the C content in the steel in the finally obtained grain-oriented electrical steel sheet increases. In addition, since there is a close relationship between decarburization and the development of an internal oxide layer, if the decarburization is insufficient, an ideal internal oxide layer cannot be obtained, resulting in poor film adhesion. It is speculated that
- the present invention has been made based on the above findings, and its gist and configuration is as follows.
- a steel slab for a grain-oriented electrical steel sheet is hot-rolled into a hot-rolled steel sheet, The hot-rolled steel sheet is cold-rolled once or twice or more with intermediate annealing to obtain a cold-rolled steel sheet, Pickling the cold-rolled steel sheet, subjecting the cold-rolled steel sheet to decarburization annealing, An annealing separator containing MgO is applied to the surface of the cold-rolled steel sheet after the decarburization annealing, A method for producing a grain-oriented electrical steel sheet, comprising subjecting the cold-rolled steel sheet coated with the annealing separator to finish annealing, In the pickling, using a solution having an acid concentration of 1.0% by mass or more and 20% by mass or less and an Fe ion concentration of 2% by mass or more and 15% by mass or less, A method for producing a grain-oriented electrical steel sheet, wherein in the decarburization annealing, the concentration of CO, which is inevitably mixed in the atmospheric gas, is maintained at 6% by volume or less
- a grain-oriented electrical steel sheet with excellent coating adhesion can be obtained.
- 4 is a graph showing the relationship between Fe ion concentration and film adhesion. 4 is a graph showing the relationship between acid concentration and film adhesion. 4 is a graph showing the relationship between in-furnace CO concentration, film adhesion, and C content in steel.
- a steel slab for grain-oriented electrical steel sheets (hereinafter sometimes simply referred to as a steel slab) is used as a starting material.
- a steel slab having any chemical composition can be used without any particular limitation.
- the steel slab preferably contains the following components.
- “%” represents “mass %” and “ppm” represents “mass ppm”.
- the C content is preferably 0.10% or less, more preferably 0.06% or less.
- the C content is preferably 0.01% or more, more preferably 0.03% or more.
- Si 2.0% or more and 5.0% or less Si is an effective element for increasing the resistivity of steel and improving iron loss. If the Si content is less than 2.0%, the effect is poor. Therefore, the Si content is preferably 2.0% or more, more preferably 3.0% or more. On the other hand, if the Si content exceeds 5.0%, the workability of the steel deteriorates, making rolling difficult. Therefore, the Si content is preferably 5.0% or less, more preferably 3.6% or less.
- Mn 0.01% or more and 0.50% or less Mn is an effective element for improving hot workability. If the Mn content is less than 0.01%, the effect is poor. Therefore, the Mn content is preferably 0.01% or more, more preferably 0.03% or more. On the other hand, when the Mn content exceeds 0.50%, the magnetic flux density of the grain-oriented electrical steel sheet decreases. Therefore, the Mn content is preferably 0.50% or less, more preferably 0.15% or less.
- the chemical composition of the steel slab may further contain one or both of S and Se in a total amount of 0.005% or more and 0.10% or less. can.
- the chemical composition of the steel slab can further include Al: 0.01% or more and 0.04% or less and N: 0.003% or more and 0.012% or less.
- the content of Al, N, S, and Se can be reduced as much as possible, and the Goss orientation can be secondary recrystallized by the texture inhibition effect. Therefore, it is preferable to reduce the contents of Al, N, S, and Se in the chemical composition of the steel slab to the following ranges. Al: 0.010% or less N: 0.0060% or less S and Se: total 0.010% or less
- the lower limit of the content of these elements may be 0%.
- the contents of Al, N, S, and Se are within the following ranges.
- C 0.01 to 0.10%
- Si 2.0 to 5.0%
- Mn 0.01-0.50%
- Al 0-0.04%
- N 0 to 0.012%
- S and Se total 0 to 0.10%
- a steel slab having a chemical composition in which the balance is Fe and unavoidable impurities can be used.
- the above component composition further optionally includes Ni: 0 to 1.50%, Cr: 0 to 0.50%, Cu: 0-0.50%, P: 0 to 0.50%, Sb: 0 to 0.50%, Sn: 0-0.50%, Bi: 0 to 0.50%, Mo: 0-0.50%, B: 0 to 25 ppm, Nb: 0 to 0.020%, V: 0 to 0.010%, Zr: 0 to 0.10%, Co: 0-0.050%, Pb: 0 to 0.0100%, As: 0 to 0.0200%, Zn: 0-0.020%, W: 0 to 0.0100%, One or more selected from the group consisting of Ge: 0 to 0.0050% and Ga: 0 to 0.0050% can also be contained. By adding these elements, the magnetic properties can be further improved. However, if the content exceeds the upper limit, the growth of secondary recrystallized grains is suppressed, so the magnetic properties are rather deteriorated.
- the lower limit of the content is set to 0%.
- the contents of the above elements are each independently set to be equal to or higher than the lower limit values below.
- the method of manufacturing the steel slab is also not particularly limited, and it can be manufactured by any method.
- a steel slab can be produced by an ingot casting method or a continuous casting method using molten steel adjusted to a predetermined chemical composition. It is also possible to use the direct casting method to produce a thin slab having a thickness of 100 mm or less and use it as a steel slab.
- the steel slab is hot rolled into a hot rolled steel sheet.
- the steel slab may be heated prior to the hot rolling, or the steel slab may be rolled immediately without reheating after the steel slab is obtained by casting.
- the slab heating temperature before hot rolling is not particularly limited, it is preferably 1100 to 1460°C.
- the slab heating temperature is preferably 1300° C. or higher in order to completely dissolve the inhibitor component.
- the hot rolling conditions are not particularly limited, and can be carried out under any conditions. From the viewpoint of controlling the structure of the hot-rolled steel sheet, in the hot rolling, one pass or more of rough rolling is performed at 900 ° C. or higher and 1200 ° C. or lower, and then two or more passes are performed at 700 ° C. or higher and 1000 ° C. or lower. Rolling is preferred.
- the obtained hot-rolled steel sheet may be wound into a coil shape.
- the winding temperature it is preferable to set the winding temperature to 400° C. or more and 750° C. or less from the viewpoint of both control of carbide structure and prevention of defects such as cracks. More preferably, the winding temperature is 500° C. or higher and 700° C. or lower.
- the obtained hot-rolled steel sheet is subjected to hot-rolled sheet annealing.
- hot-rolled sheet annealing By performing hot-rolled sheet annealing, it is possible to homogenize the structure of the steel sheet and reduce variations in the magnetic properties of the finally obtained grain-oriented electrical steel sheet.
- the annealing temperature is preferably 800° C. or higher and 1250° C. or lower, more preferably 900° C. or higher and 1150° C. or lower, from the viewpoint of homogenizing the structure.
- the hot-rolled sheet annealing from the viewpoint of homogenizing the structure, it is preferable to maintain the temperature after heating to the heating temperature.
- the holding time is preferably 5 seconds or more, and more preferably 10 seconds or more and 180 seconds or less.
- the steel plate may be cooled.
- the cooling rate in the temperature range from 800 ° C. to 350 ° C. is preferably 5 ° C./s or more and 100 ° C./s or less, and 15 ° C./s or more and 45 ° C./s. s or less is more preferable.
- the descaling method is not particularly limited, and any method can be adopted. For example, a method using heated acid, a method of mechanically removing scales, or the like can be used.
- the hot-rolled steel sheet is cold-rolled once or twice or more with intermediate annealing, to obtain a cold-rolled steel sheet.
- Conditions for the cold rolling are not particularly limited, and any conditions can be used.
- the cold rolling it is preferable to use a lubricant such as rolling oil in order to reduce the rolling load and improve the rolling shape.
- a lubricant such as rolling oil
- the total rolling reduction in the last cold rolling (hereinafter referred to as final cold rolling) of the cold rolling is set to 50%. It is preferable to make it 92% or less.
- the cooling rate from 900 ° C. to 350 ° C. is preferably 5 ° C./s or more and 100 ° C./s or less from the viewpoint of controlling the morphology of the second phase and precipitates, and is 15 ° C./s. It is more preferable to set the temperature to 45° C./s.
- rolling oil may adhere to the rolled steel plate. Therefore, when intermediate annealing is performed, it is preferable to perform degreasing prior to the intermediate annealing to remove the rolling oil. Moreover, after the intermediate annealing, it is preferable to perform descaling in order to remove the scale formed on the surface of the steel sheet.
- the descaling method is not particularly limited, and any method can be adopted. For example, a method using heated acid, or mechanical scale removal can be used.
- the obtained cold-rolled steel sheet is preferably degreased prior to the next pickling.
- decarburization annealing is applied to the cold-rolled steel sheet after the pickling.
- Conditions for the decarburization annealing are not particularly limited, and any conditions can be used.
- the temperature range of 750° C. to 950° C. is preferably maintained for 10 seconds or longer, and the temperature range of 800° C. to 900° C. is more preferably maintained for 10 seconds or longer.
- the decarburization annealing is preferably performed in a moist atmosphere containing H2 and N2 .
- the dew point of the moist atmosphere is preferably 20° C. or higher and 80° C. or lower, more preferably 40° C. or higher and 70° C.
- the concentration of CO which is unavoidably mixed in the ambient gas, is maintained at 6% by volume or less.
- an annealing separator containing MgO is applied to the surface of the cold-rolled steel sheet after the decarburization annealing.
- the annealing separator it is preferable to use an annealing separator containing MgO as a main component.
- the content of MgO in the annealing separator is preferably 60% by mass or more.
- the application of the annealing separator is not particularly limited, it is generally preferable to apply it to both surfaces of the cold-rolled steel sheet.
- the coating amount of the annealing separator is preferably 2.5 g/m 2 or more per side.
- the application of the annealing separator may be performed by a wet method or a dry method.
- a slurry containing MgO can be applied.
- electrostatic coating can be used.
- the slurry temperature it is preferable to set the slurry temperature at a constant temperature of 5° C. or higher and 30° C. or lower in order to suppress an increase in viscosity.
- the cold-rolled steel sheet coated with the annealing separator is subjected to finish annealing to develop secondary recrystallized grains and form a forsterite coating.
- the finish annealing can be performed under arbitrary conditions without being particularly limited.
- Finish annealing is typically carried out in a state in which the cold-rolled steel sheet to which the annealing separator is applied is wound into a coil. Since finish annealing generally takes a long time, it is preferable to anneal the coil in an up-end state.
- the up-end state is a state in which the central axis of the coil is in the vertical direction.
- the annealing temperature in the final annealing is preferably 800°C or higher. Furthermore, from the viewpoint of sufficiently advancing the formation of the forsterite coating, the annealing temperature is preferably 1050° C. or higher. On the other hand, the upper limit of the annealing temperature in the finish annealing is also not particularly limited, but from the viewpoint of preventing buckling of the coil, it is preferably 1300° C. or less.
- the finish annealing can also serve as purification annealing for removing inhibitor-forming elements from the steel.
- the annealing separator After finish annealing, it is preferable to remove the annealing separator remaining on the surface of the steel sheet.
- the removal of the annealing separator can be performed by, for example, washing with water, brushing, pickling, or the like.
- the insulating coating is preferably a tension coating capable of applying tension to the steel plate.
- the method of forming the insulating coating is not particularly limited, and can be formed by any method.
- the insulating coating can be formed by applying a coating liquid to the surface of the grain-oriented electrical steel sheet and baking it.
- a coating liquid may be applied before flattening annealing, and baked by flattening annealing.
- the insulating coating may be provided via a binder. From the same point of view, it is also possible to vapor-deposit an inorganic material on the steel sheet surface layer by physical vapor deposition or chemical vapor deposition to form an insulating coating.
- Example 1 A grain-oriented electrical steel sheet having a forsterite coating and an insulating coating on its surface was manufactured by the following procedure.
- a steel slab for grain-oriented electrical steel sheets containing C: 0.056%, Si: 3.24%, and Mn: 0.07% by mass was heated to a temperature of 1400°C and subjected to hot rolling.
- a hot-rolled steel sheet having a thickness of 2.3 mm was obtained.
- the pickled hot-rolled steel sheet is first cold-rolled to a thickness of 1.6 mm, subjected to intermediate annealing at 1050 ° C. for 100 seconds, and then cold-rolled for the second time to obtain a sheet.
- a cold-rolled steel sheet having a thickness of 0.23 mm was used.
- the cold-rolled steel sheet was pickled in a hydrochloric acid solution at a temperature of 60°C.
- the acid concentration and Fe ion concentration in the hydrochloric acid solution were as shown in Table 1.
- the acid concentration and Fe ion concentration were measured using an ultrasonic densitometer manufactured by Fuji Kogyo Co., Ltd.
- the Fe ions in the hydrochloric acid solution were added as iron(III) chloride hexahydrate. Further, when the hydrochloric acid solution is used for pickling, the Fe ion concentration increases with the elution of iron from the cold-rolled steel sheet. Therefore, the Fe ion concentration was kept constant by adding the hydrochloric acid aqueous solution while monitoring the Fe ion concentration of the hydrochloric acid solution using the ultrasonic concentration measuring device.
- the pickled cold-rolled steel sheet was subjected to decarburization annealing at 860°C for 120 seconds in 50% H 2 +50% N 2 with a dew point of 60°C.
- the CO concentration in the annealing furnace was controlled to the values shown in Table 1.
- a MgO-based annealing separator was applied to the surface of the steel sheet, and finish annealing was performed at 1220 ° C. for 10 hours in an H atmosphere to form a forsterite coating on the steel sheet surface. .
- finish annealing was performed at 1220 ° C. for 10 hours in an H atmosphere to form a forsterite coating on the steel sheet surface.
- a coating liquid mainly containing phosphate was applied.
- the steel plate to which the coating solution was applied was subjected to flattening annealing, which serves both coating baking and flattening of the steel plate, to form an insulating coating on the surface of the steel plate.
- the annealing temperature in the flattening annealing was 780° C., and the annealing time was 30 seconds.
- the film adhesion of the obtained grain-oriented electrical steel sheets was evaluated.
- the film adhesion was evaluated by winding grain-oriented electrical steel sheets around cylinders having various diameters and determining the minimum diameter at which the film did not peel off. The smaller the minimum diameter, the better the film adhesion.
- C content in steel The amount of C in the steel of the obtained grain-oriented electrical steel sheets was measured. The measurement of the amount of C in the steel was carried out after the film present on the surface of the grain-oriented electrical steel sheet was removed by pickling with hydrochloric acid of 5% concentration at 90°C.
- iron loss The iron loss of the obtained grain-oriented electrical steel sheets was measured by a method based on JIS C2550-1 (2011).
- Example 2 A steel slab for grain-oriented electrical steel sheets containing 0.049% by mass, C: 0.049%, Si: 3.11%, Mn: 0.10%, Se: 0.015%, and Sb: 0.15%, 1400 °C and hot-rolled to form a hot-rolled steel sheet with a thickness of 2.6 mm. Next, pickling was performed to remove scales on the surface of the hot-rolled steel sheet.
- the pickled hot-rolled steel sheet is first cold-rolled to a thickness of 0.58 mm, subjected to intermediate annealing at 1000 ° C. for 30 seconds, and then cold-rolled for the second time to obtain a sheet.
- a cold-rolled steel sheet having a thickness of 0.23 mm was used.
- the cold-rolled steel sheet was pickled.
- acid solutions having the types and acid concentrations shown in Table 2 were used.
- the acid solution had a temperature of 75° C. and an Fe ion concentration of 3%.
- the acid concentration and Fe ion concentration were measured using an ultrasonic densitometer manufactured by Fuji Kogyo Co., Ltd.
- Other conditions for the pickling were the same as in Example 1 above.
- decarburization annealing was performed at 840°C for 120 seconds, 50% H 2 +50% N 2 , and a dew point of 60°C. At this time, the CO concentration in the annealing furnace was controlled to 5.0%.
- the surface of the steel sheet was coated with an annealing separation agent mainly composed of MgO, and subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- an annealing separation agent mainly composed of MgO was applied, and flattening annealing was performed to bake the coating and flatten the steel sheet.
- the annealing temperature in the flattening annealing was 840° C., and the annealing time was 60 seconds.
- the film adhesion, the amount of C in the steel, and the iron loss of the obtained grain-oriented electrical steel sheets were evaluated in the same manner as in Example 1 above.
- the obtained results are also shown in Table 2. From the results shown in Table 2, it can be seen that the method of the present invention provides a grain-oriented electrical steel sheet having excellent film adhesion and core loss properties and having a C content in the steel that does not cause magnetic aging.
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Abstract
Description
質量%で、C:0.048%、Si:3.44%、Mn:0.10%を含む方向性電磁鋼板用鋼スラブを、1400℃の温度に加熱し、熱間圧延を施して板厚3.0mmの熱延鋼板とした。前記熱延鋼板に対して950℃で40秒の熱延板焼鈍を施した後、酸洗を行って鋼板表面のスケールを除去した。
質量%で、C:0.075%、Si:2.88%、Mn:0.05%、Se:0.019%、Sb:0.08%を含む方向性電磁鋼板用鋼スラブを、1380℃の温度に加熱し、熱間圧延を施して板厚2.4mmの熱延鋼板とした。次いで、酸洗を行って前記熱延鋼板表面のスケールを除去した。
質量%で、C:0.082%、Si:3.51%、Mn:0.23%、Al:0.029%、N:0.008%、Se:0.012%、S:0.004%を含む方向性電磁鋼板用スラブを、1420℃の温度に加熱し、熱間圧延を施して板厚2.5mmの熱延鋼板とした。前記熱延鋼板に対して950℃で30秒の熱延板焼鈍を施した後、酸洗を行って鋼板表面のスケールを除去した。
前記熱延鋼板に対して、1回または中間焼鈍を挟む2回以上の冷間圧延を施して冷延鋼板とし、
前記冷延鋼板を酸洗し、
前記冷延鋼板に脱炭焼鈍を施し、
前記脱炭焼鈍後の前記冷延鋼板の表面に、MgOを含有する焼鈍分離剤を塗布し、
前記焼鈍分離剤が塗布された前記冷延鋼板に仕上焼鈍を施すことを含む、方向性電磁鋼板の製造方法であって、
前記酸洗においては、酸濃度:1.0質量%以上20質量%以下、かつFeイオン濃度:2質量%以上15%質量以下の溶液を使用し、
前記脱炭焼鈍においては、雰囲気ガス中に不可避に混入するCOの濃度を6体積%以下に維持することを特徴とする、方向性電磁鋼板の製造方法。
本発明においては、出発材料として方向性電磁鋼板用鋼スラブ(以下、単に鋼スラブという場合がある)を使用する。前記鋼スラブとしては、とくに限定されることなく任意の成分組成を有する鋼スラブを使用することができる。
C含有量が0.10%より高いと、脱炭焼鈍を施しても、鋼中C量を磁気時効の起こらない0.0035%以下まで低減することが困難となる。そのため、C含有量は0.10%以下とすることが好ましく、0.06%以下とすることがより好ましい。一方、C含有量が0.01%に満たないと、Cによる粒界強化効果が失われ、鋼スラブにクラックが生じるなどの欠陥が生じ、操業性に支障がでる可能性がある。そのため、C含有量は0.01%以上とすることが好ましく、0.03%以上とすることがより好ましい。
Siは鋼の比抵抗を高め、鉄損を改善させるために有効な元素である。Si含有量が2.0%未満であるとその効果が乏しい。そのため、Si含有量は2.0%以上とすることが好ましく、3.0%以上とすることがより好ましい。一方、Si含有量が5.0%を超えると鋼の加工性が劣化し、圧延が困難となる。そのため、Si含有量は5.0%以下とすることが好ましく、3.6%以下とすることがより好ましい。
Mnは熱間加工性を良好にするために有効な元素である。Mn含有量が0.01%未満であるとその効果が乏しい。そのため、Mn含有量は0.01%以上とすることが好ましく、0.03%以上とすることがより好ましい。一方、Mn含有量が0.50%を超えると方向性電磁鋼板の磁束密度が低下する。そのため、Mn含有量は0.50%以下とすることが好ましく、0.15%以下とすることがより好ましい。
Al:0.010%以下
N:0.0060%以下
SおよびSe:合計0.010%以下
Al:0%以上0.008%以下
N:0%以上0.0050%以下
SおよびSe:合計0%以上0.005%未満
C :0.01~0.10%、
Si:2.0~5.0%、
Mn:0.01~0.50%、
Al:0~0.04%、
N :0~0.012%、および
SおよびSe:合計0~0.10%を含み、
残部がFeおよび不可避的不純物である成分組成を有する鋼スラブを用いることができる。
Ni:0~1.50%、
Cr:0~0.50%、
Cu:0~0.50%、
P :0~0.50%、
Sb:0~0.50%、
Sn:0~0.50%、
Bi:0~0.50%、
Mo:0~0.50%、
B :0~25ppm、
Nb:0~0.020%、
V :0~0.010%、
Zr:0~0.10%、
Co:0~0.050%、
Pb:0~0.0100%、
As:0~0.0200%、
Zn:0~0.020%、
W :0~0.0100%、
Ge:0~0.0050%、および
Ga:0~0.0050%からなる群より選択される1または2以上を含有することもできる。これらの元素を添加することにより、磁気特性をさらに向上させることができる。しかし、含有量が上限値を超えると二次再結晶粒の発達が抑制されるため、かえって磁気特性が劣化する。
Ni:0.01%、
Cr:0.01%、
Cu:0.01%、
P :0.005%、
Sb:0.005%、
Sn:0.005%、
Bi:0.005%、
Mo:0.005%、
B :2ppm、
Nb:0.001%、
V :0.001%、
Zr:0.001%、
Co:0.002%、
Pb:0.0001%、
As:0.0010%、
Zn:0.001%、
W :0.0010%、
Ge:0.0001%、および
Ga:0.0001%。
次に、前記鋼スラブを熱間圧延して熱延鋼板とする。なお、前記熱間圧延に先だって、鋼スラブを加熱してもよく、また、鋳造によって鋼スラブを得た後、再加熱せずに直ちに圧延を施してもよい。熱間圧延前のスラブ加熱温度は特に限定されないが、1100~1460℃とすることが好ましい。特に、鋼スラブがインヒビタ成分を含まない場合には前記スラブ加熱温度を1300℃以下とすることがコストの観点で好ましい。また、インヒビタ成分を含む場合は、インヒビタ成分を完全固溶させるために前記スラブ加熱温度を1300℃以上とすることが好ましい。
次いで、前記熱延鋼板に対して、1回または中間焼鈍を挟む2回以上の冷間圧延を施して冷延鋼板とする。前記冷間圧延の条件はとくに限定されず、任意の条件で行うことができる。
本発明では、冷延鋼板に対して、酸濃度:1.0%以上20%以下、かつFeイオン濃度:2%以上15%以下の溶液を使用して酸洗を施すことが重要である。先に述べたように、前記条件で酸洗を行うことにより、優れた被膜密着性を得ることができる。
次いで、前記酸洗後の冷延鋼板に脱炭焼鈍を施す。前記脱炭焼鈍の条件はとくに限定されず、任意の条件で行うことができる。前記脱炭焼鈍においては、750℃以上950℃以下の温度域で10秒以上保持することが好ましく、800℃以上900℃以下の温度域で10秒以上保持することがより好ましい。前記脱炭焼鈍は、H2とN2とを含む、湿潤雰囲気中で行うことが好ましい。前記湿潤雰囲気の露点は、脱炭焼鈍の一部もしくはすべての範囲において、20℃以上80℃以下とすることが好ましく、40℃以上70℃以下とすることがより好ましい。前記脱炭焼鈍においては、雰囲気ガス中にCOが不可避に混入するが、上述した理由により、炉内CO濃度を6%以下とする必要がある。炉内CO濃度を6%以下に制御することにより、優れた被膜密着性が得られるとともに、鋼中C量を35ppm以下とすることができる。そのため、前記脱炭焼鈍においては、雰囲気ガス中に不可避に混入するCOの濃度を6体積%以下に維持する。
その後、前記脱炭焼鈍後の冷延鋼板の表面に、MgOを含有する焼鈍分離剤を塗布する。前記焼鈍分離剤としては、MgOを主成分として含有する焼鈍分離剤を用いることが好ましい。前記焼鈍分離剤におけるMgOの含有量は、60質量%以上であることが好ましい。
その後、前記焼鈍分離剤が塗布された冷延鋼板に仕上焼鈍を施すことにより、二次再結晶粒を発達させるとともにフォルステライト被膜を形成する。前記仕上焼鈍は、とくに限定されることなく任意の条件で行うことができる。
以下の手順で、表面にフォルステライト被膜と絶縁コーティングとを備える方向性電磁鋼板を製造した。
得られた方向性電磁鋼板の被膜密着性を評価した。前記被膜密着性は、方向性電磁鋼板を種々の直径を有した円筒に巻き付けて、被膜が剥がれない最小径を求めることによって評価した。この最小径が小さいほど被膜密着性が優れる。
得られた方向性電磁鋼板の鋼中C量を測定した。前記鋼中C量の測定は、5%濃度、90℃の塩酸で酸洗することにより方向性電磁鋼板の表面に存在する被膜を除去した後に実施した。
得られた方向性電磁鋼板の鉄損を、JIS C2550-1(2011)に準拠した方法で測定した。
質量%で、C:0.049%、Si:3.11%、Mn:0.10%、Se:0.015%、Sb:0.15%を含む方向性電磁鋼板用鋼スラブを、1400℃の温度に加熱し、熱間圧延を施して板厚2.6mmの熱延鋼板とした。次いで、酸洗を行って前記熱延鋼板表面のスケールを除去した。
Claims (2)
- 方向性電磁鋼板用鋼スラブを熱間圧延して熱延鋼板とし、
前記熱延鋼板に対して、1回または中間焼鈍を挟む2回以上の冷間圧延を施して冷延鋼板とし、
前記冷延鋼板を酸洗し、
前記冷延鋼板に脱炭焼鈍を施し、
前記脱炭焼鈍後の前記冷延鋼板の表面に、MgOを含有する焼鈍分離剤を塗布し、
前記焼鈍分離剤が塗布された前記冷延鋼板に仕上焼鈍を施すことを含む、方向性電磁鋼板の製造方法であって、
前記酸洗においては、酸濃度:1.0質量%以上20質量%以下、かつFeイオン濃度:2質量%以上15%質量以下の溶液を使用し、
前記脱炭焼鈍においては、雰囲気ガス中に不可避に混入するCOの濃度を6体積%以下に維持することを特徴とする、方向性電磁鋼板の製造方法。 - 前記酸洗で使用する前記溶液に含まれる酸が、リン酸、塩酸、硫酸、および硝酸からなる群より選択される1または2以上である、請求項1記載の方向性電磁鋼板の製造方法。
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JPH09143562A (ja) * | 1995-11-27 | 1997-06-03 | Kawasaki Steel Corp | 磁気特性及び鋼板端部形状に優れるAl含有方向性電磁鋼板の製造方法 |
JP2000129356A (ja) | 1998-10-28 | 2000-05-09 | Kawasaki Steel Corp | 方向性電磁鋼板の製造方法 |
WO2018110676A1 (ja) * | 2016-12-14 | 2018-06-21 | 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 |
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JPS5113469B2 (ja) | 1972-10-13 | 1976-04-28 | ||
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JP2000129356A (ja) | 1998-10-28 | 2000-05-09 | Kawasaki Steel Corp | 方向性電磁鋼板の製造方法 |
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