WO2022250161A1 - 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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- WO2022250161A1 WO2022250161A1 PCT/JP2022/021834 JP2022021834W WO2022250161A1 WO 2022250161 A1 WO2022250161 A1 WO 2022250161A1 JP 2022021834 W JP2022021834 W JP 2022021834W WO 2022250161 A1 WO2022250161 A1 WO 2022250161A1
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- annealing
- steel sheet
- cold rolling
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- final cold
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- 229910001224 Grain-oriented electrical steel Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 137
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 119
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- 238000005097 cold rolling Methods 0.000 claims abstract description 66
- 238000005261 decarburization Methods 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 25
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
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- 150000002500 ions Chemical class 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 14
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- 230000001590 oxidative effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 238000002474 experimental method Methods 0.000 description 10
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- 229910052748 manganese Inorganic materials 0.000 description 4
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- 238000005266 casting Methods 0.000 description 3
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- 238000005098 hot rolling Methods 0.000 description 3
- 150000002506 iron compounds Chemical class 0.000 description 3
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- 239000002344 surface layer 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
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 235000021110 pickles Nutrition 0.000 description 2
- 239000010731 rolling oil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 229910052840 fayalite Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C23C22/78—Pretreatment of the material to be coated
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the present invention relates to a method for manufacturing grain-oriented electrical steel sheets.
- Electrical steel sheet is a material that is widely used as iron cores for transformers and motors. Magnetic steel sheets are roughly classified into grain-oriented magnetic steel sheets and non-oriented magnetic steel sheets.
- a grain-oriented electrical steel sheet is characterized by having 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. Such a texture is formed by causing secondary recrystallization in the final annealing. This secondary recrystallization is a phenomenon in which grain boundary energy is used to preferentially grow crystal grains of ⁇ 110 ⁇ 001> orientation, so-called Goss orientation, into giant grains.
- Patent Document 1 discloses a method using AlN or MnS
- Patent Document 2 discloses a method using MnS or MnSe, etc., which have been industrially put into practical use. The method using these inhibitors is useful for stably developing secondary recrystallized grains. , it is necessary to dissolve the inhibitor component once.
- Patent Document 3 and the like disclose a technique for developing Goss-oriented crystal grains by secondary recrystallization in a material that does not contain an inhibitor component. By eliminating impurities such as inhibitor components as much as possible, the dependence of the grain boundary energy on the grain boundary during primary recrystallization on the grain boundary misorientation angle is revealed, and the Goss orientation can be obtained without using an inhibitor. It is a technique for secondary recrystallization of grains with Since this method does not require fine dispersion of the inhibitor in the steel, it does not require high-temperature slab heating, which was essential, and thus has advantages over the method using the inhibitor in terms of production.
- the object of the present invention is to solve the problem of cracking of the steel sheet that occurs during the final cold rolling described above, and to manufacture a grain-oriented electrical steel sheet that can stably produce a grain-oriented electrical steel sheet with low iron loss. It is to provide a method.
- the slab is reheated to 1210°C and hot rolled to produce a hot-rolled sheet with a thickness of 2.4 mm.
- the hot-rolled sheet is annealed at 950°C for 10 seconds to pickle the scale on the surface of the steel sheet. removed.
- the sheet was cold-rolled to a thickness of 0.70 mm, and further subjected to intermediate annealing at 1100°C for 100 seconds.
- the atmosphere was set to 60% H 2 +40% N 2 and decarburization was performed at this point by changing the dew point to variously adjust the amount of C in the steel sheet.
- a small piece sample was taken at this point, and the layer from the surface of the steel sheet to the layer at a depth of 1/10 of the thickness of the steel sheet (hereinafter referred to as 1/10 layer) It was removed by grinding, and the average amount of C from 1/10 layer to 1/2 layer (layer at the center of plate thickness) was evaluated by the method described in JIS G1211-3:2018.
- the steel sheets were allowed to stand by at room temperature for various periods of time, and then subjected to final cold rolling to finish the sheet thickness to 0.23 mm. After that, it was pickled with hydrochloric acid at 50° C. for 5 seconds at an acid concentration of 5%.
- Iron (III) chloride hexahydrate was previously added to the treatment liquid used for the hydrochloric acid pickling to contain 5% Fe ions. During the experiment, the iron content of the steel sheet dissolved and the Fe ion concentration changed, so the concentration level was maintained by adding an aqueous solution of hydrochloric acid to the treatment liquid.
- decarburization annealing was performed at 870°C for 90 seconds, 50% H 2 +50% N 2 , dew point 60°C.
- the steel sheet was subjected to final annealing at 1200° C. for 20 hours in an H 2 atmosphere.
- a coating solution mainly composed of phosphate was applied, and the coating was baked at 850°C for 50 seconds and the steel sheet was flattened. Flattening annealing was applied.
- FIG. 1 shows a graph in which the results are organized by the amount of C in the steel after intermediate annealing and the time from immediately after the completion of intermediate annealing to immediately before the start of final cold rolling (hereinafter also referred to as waiting time).
- waiting time As is clear from the figure, when the waiting time from immediately after intermediate annealing to immediately before the start of final cold rolling is long, the number of defects tends to be large, and the larger the amount of C after intermediate annealing, the more the number of defects is 3. It can be seen that the waiting time exceeding
- condition B the number of defects is 4.8 per 1000 m, which is a large deviation from the number and frequency of coarse carbides obtained from the above observation results. presumed to be low. Therefore, it is considered that condition B is more likely to cause such carbides than condition A.
- the number of defects is set to 3 as the threshold.
- a defect occurs in the steel sheet, it is necessary to remove the defect with a slitter line or the like. Upon removal, the coil is split. Assuming that 3 defects are evenly distributed in the length of 1000m, the calculation is that the 1000m coil is divided into 4 coils of 250m. Assuming a 250 m coil with a thickness of 0.23 mm and a width of 1200 mm, the weight is about 0.55 tons.
- a general slitter line is designed to handle coils of about 10 to 40 tons, and if the coil to be handled is less than 0.5 tons, the threading and controllability of the above line will be significantly deteriorated. In order to prevent such problems from occurring, it is necessary to suppress the number of defects per 1000 m to 3 or less.
- the size of carbides affects the C content in the steel after decarburization annealing and, in turn, the C content in the product sheet.
- C in the steel diffuses into the surface layer of the steel sheet, and then becomes CO and CO 2 under the influence of the furnace atmosphere and is eliminated from the steel.
- the carbide is coarse, the diffusion of C starts from the surface layer of the carbide, but the inside remains in place, so decarburization may be suppressed.
- decarburization was performed under the conditions on the boundary between ⁇ and ⁇ (dotted line) in FIG.
- Experiment 2 was performed by changing the pickling conditions before annealing.
- the steel sheet was subjected to final annealing at 1200° C. for 20 hours in an H 2 atmosphere.
- a coating solution mainly composed of phosphate was applied, and the coating was baked at 850°C for 50 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the amount of base iron C in the final product sheet was analyzed by the method described in JIS G1211-3:2018.
- ⁇ indicates that the magnetic aging can be suppressed at 50 ppm or less
- x indicates that it exceeds 50 ppm. From the figure, it can be seen that in order to achieve a C content in the steel that does not cause magnetic aging, the hydrochloric acid concentration must be 1% or more and 20% or less and the Fe ion concentration must be 2% or more and 15% or less.
- the present inventors defined the time from immediately after annealing before final cold rolling to immediately before the start of final cold rolling, and performed pickling treatment before decarburization annealing. It was newly discovered that by adding Fe ions to the liquid at a certain rate, defects that occur during the final cold rolling can be effectively prevented, the amount of C in the product sheet can be reduced, and magnetic aging can be suppressed.
- the present invention is based on the above findings. That is, the gist and configuration of the present invention are as follows. 1. A steel material 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 having a final thickness, and then the cold-rolled steel sheet is decarburizing annealing, applying an annealing separator to the surface of the steel sheet, and then performing finish annealing, In the steel sheet after annealing before the final cold rolling and before the final cold rolling, the depth from the surface of the steel sheet is the average of the area from 1/10 to 1/2 of the thickness of the steel sheet When the amount of C is A (% by mass) and the time from immediately after the completion of annealing performed before the final cold rolling to just before the start of the final cold rolling is T (time), T ⁇ -4000 x A + 440 and T ⁇ 360 The filling, After the final cold rolling and before the decarburization annea
- the cold rolling in the case of one time and the last cold rolling in the case of two or more times are the final cold rollings.
- the annealing performed immediately before the final cold rolling is the annealing performed before the final cold rolling.
- the annealing before the final cold rolling is the hot-rolled sheet annealing in the case of one cold rolling, and the intermediate annealing in the case of two or more cold rollings.
- the decarburization annealing is divided into pre-stage annealing and post-stage annealing,
- the pre-annealing is performed in an annealing atmosphere in which the atmosphere oxidizing P(H 2 O)/P(H 2 ) is 0.3 or more and 0.7 or less
- the post-annealing is performed in the atmosphere oxidizing P(H 2 O)/P 3.
- the present invention it is possible to stably produce a grain-oriented electrical steel sheet with low iron loss because it is possible to prevent defects that occur during the final cold rolling, reduce the amount of the product sheet C, and suppress magnetic aging. can.
- FIG. 2 is a diagram showing the relationship between the amount of C in steel after intermediate annealing, the time from immediately after intermediate annealing to immediately before the start of final cold rolling, and the number of defects after final cold rolling.
- FIG. 4 is a diagram showing the relationship between the pickling conditions and the base iron C content of the final product sheet.
- C 0.01% or more and 0.10% or less If C exceeds 0.10%, it becomes difficult to reduce it to 50 ppm or less at which magnetic aging does not occur after decarburization annealing. On the other hand, if the content is less than 0.01%, the grain boundary strengthening effect of C may be lost, and defects such as cracks in the slab may occur, which may hinder workability. Therefore, C is preferably 0.01% or more and 0.10% or less. More preferably, it is 0.03% or more and 0.06% or less.
- Si 2.0% to 5.0% Si is a useful element for increasing the resistivity of steel and improving iron loss, but if it is less than 2.0%, the effect is poor. On the other hand, if it exceeds 5.0%, there is a fear that the workability of steel deteriorates and rolling becomes difficult. Therefore, Si is preferably 2.0% or more and 5.0% or less. More preferably, it is 3.0% or more and 3.6% or less.
- Mn 0.01% or more and 0.50% or less Mn is a useful element for improving hot workability. On the other hand, if it exceeds 0.50%, the magnetic flux density of the product sheet is lowered, so 0.50% or less is preferable. More preferably, it is 0.03% or more and 0.15% or less.
- MnS and MnSe when using MnS and MnSe, in addition to the above Mn amount, one or two of S and Se are included in a total amount of 0.005% or more and 0.100% or less. be able to.
- AlN when AlN is used, Al: 0.01% or more and 0.04% or less and N: 0.003% or more and 0.010% or less can be included.
- both MnS or MnSe and AlN are used, they can be used together.
- the present invention can contain other optional components, and specifically, the elements described below can be appropriately contained. That is, for the purpose of improving the magnetic properties, Ni: more than 0% and 1.50% or less, Cr: more than 0% and 0.50% or less, Cu: more than 0% and 0.50% or less, P: more than 0% and 0.50% or less, Sb: 0% more than 0.50%, Sn: more than 0% and less than 0.50%, Bi: more than 0% and less than 0.50%, Mo: more than 0% and less than 0.50%, B: more than 0 ppm and less than 25 ppm, Nb: more than 0% and less than 0.020%, V: More than 0% and 0.010% or less, Zr: more than 0% and 0.10% or less, Co: more than 0% and 0.050% or less, Pb: more than 0% and 0.0100% or less, As: more than 0% and 0.0200% or less, Zn: more than 0%
- the steel material of the present invention can have a chemical composition containing the above basic components and optionally the above optional components, with the balance being Fe and unavoidable impurities.
- steel material C 0.01% or more and 0.10% or less, Si: 2.0% or more and 5.0% or less, Mn: 0.01% or more and 0.50% or less, and ⁇ group: Al: 0.01% or more and 0.04% or less and N: 0.003% or more and 0.010% or less, and ⁇ group: either one or two of S or Se, totaling 0.005% It can have a component composition containing either or both of more than or equal to 0.100% or less, with the balance being Fe and unavoidable impurities.
- the steel material C 0.01% or more and 0.10% or less, Si: 2.0% or more and 5.0% or less, Mn: 0.01% or more and 0.50% or less, Al: 0.010% or less, N: 0.0060% or less, and one or two of S and Se in total of 0.010% or less, with the balance being Fe and unavoidable impurities.
- the above steel materials are further Ni: more than 0% and 1.50% or less, Cr: more than 0% and 0.50% or less, Cu: more than 0% and 0.50% or less, P: more than 0% and 0.50% or less, Sb: more than 0% and 0.50% or less, Sn: more than 0% and 0.50% or less, Bi: more than 0% and 0.50% or less, Mo: more than 0% and 0.50% or less, B: more than 0 ppm and 25 ppm or less, Nb: more than 0% and 0.020% or less, V: more than 0% and 0.010% or less, Zr: more than 0% and 0.10% or less, Co: more than 0% and 0.050% or less, Pb: more than 0% and 0.0100% or less, As: more than 0% and 0.0200% or less, Zn: more than 0% and 0.020% or less, W: more than 0% and 0.0100% or less, It may contain one or more selected from the group consisting of Ge:
- Molten steel having the above components may be used to produce slabs by ordinary ingot casting or continuous casting, or may be produced by direct casting into thin flakes with a thickness of 100 mm or less. These slabs and thin cast pieces as steel materials are hot rolled after being heated by an ordinary method, but may be hot rolled immediately after casting without heating.
- As for the above heating temperature in the case of a component system using an inhibitor, it is preferable to heat at 1300° C. or higher to dissolve the inhibitor component into a solid solution. On the other hand, when the inhibitor is not used, heating at 1300° C. or less is preferable from the viewpoint of cost.
- one pass or more of rough rolling is performed at 900°C or more and 1200°C or less, followed by two or more passes of finish rolling at 700°C or more and 1000°C or less. is preferred.
- the winding temperature it is preferable to set the winding temperature to 400° C. or higher and 750° C. or lower from the viewpoint of both controlling the carbide structure and preventing defects such as cracks. More preferably, the temperature is 500°C or higher and 700°C or lower.
- hot-rolled sheet annealing can be applied as needed.
- the structure can be homogenized, and variations in magnetic properties can be reduced.
- the hot-rolled sheet be annealed at 800° C. or higher and 1250° C. or lower for 5 seconds or longer.
- the temperature is maintained at 900° C. or higher and 1150° C. or lower for 10 seconds or longer and 180 seconds or shorter.
- Cooling after holding is preferably at a cooling rate of 5°C/s or more and 100°C/s or less in the temperature range from 800°C to 350°C from the viewpoint of controlling the morphology of the second phase and precipitates. More preferably, it is 15°C/s or more and 45°C/s or less.
- the steel sheet is subjected to cold rolling once or twice or more with intermediate annealing to obtain the final sheet thickness, and then decarburization annealing is performed.
- intermediate annealing it is preferable from the viewpoint of structure control to hold the steel in the temperature range of 800° C. or higher and 1250° C. or lower for 5 seconds or longer. In the cooling after holding in this intermediate annealing, the cooling rate from 800° C. to 350° C.
- the steel sheet is preferably degreased in order to remove the rolling oil from the preceding process. On the other hand, after intermediate annealing, it is preferable to remove the scale on the surface of the steel sheet.
- the method may be a known method such as a method using heated acid or mechanical scale removal.
- a lubricant such as rolling oil in order to reduce the rolling load and improve the rolling shape. Further, it is preferable to set the total rolling reduction in the final cold rolling to 50% or more and 92% or less in order to obtain a good recrystallized texture before secondary recrystallization.
- the steel plate after annealing before final cold rolling and before final cold rolling is reduced from 1/10 layer to 1/10 layer.
- A mass%
- T time
- the cold-rolled steel sheet after final cold rolling is subjected to decarburization annealing, but in the present invention, it is essential to perform pickling treatment before decarburization annealing. In this case, it is essential to carry out the pickling treatment with a treatment solution having an acid concentration of 1% to 20% and an Fe ion content of 2% to 15% for the reasons described above.
- the acid of the treatment liquid is not particularly limited, and may be phosphoric acid, hydrochloric acid, sulfuric acid or nitric acid.
- the acid may be used alone or in combination of two or more, and is preferably used in the form of an aqueous solution.
- the Fe ion content of the treatment liquid can be adjusted by adding an iron compound to the treatment liquid.
- Iron compounds include iron (III) chloride hexahydrate, iron (III) phosphate, and the like. The iron compounds may be used singly or in combination of two or more.
- the Fe ion concentration can be calculated by measuring the electrical conductivity, liquid temperature, and ultrasonic propagation velocity of the acid solution using, for example, an ultrasonic concentration measuring device.
- the acid concentration and the Fe ion concentration were measured using an ultrasonic concentration measuring device manufactured by Fuji Kogyo Co., Ltd.
- the iron content of the steel sheet dissolves during the treatment and the Fe concentration in the treatment solution fluctuates, it is preferable to keep the Fe concentration constant by adding an acid aqueous solution.
- the acid the acid exemplified as the treatment acid can be used.
- Decarburization annealing is carried out in a temperature range of 750°C or higher and 950°C or lower for 10 seconds or more, the atmospheric gas contains H 2 and N 2 , and the dew point is 20°C or higher in part or all of the decarburization annealing.
- a wet atmosphere of 80° C. or less is preferable. More preferably, the temperature is 800° C. or higher and 900° C. or lower, and the dew point is 30° C. or higher and 70° C. or lower.
- decarburization annealing is divided into pre - annealing and post-annealing.
- (H 2 O) / P (H 2 ) is performed in an annealing atmosphere of 0.005 or more and 0.20 or less, so that part of the fayalite near the surface formed by high oxidation annealing is low oxidation. It is preferable because it changes to silica when it is annealed and the film properties are improved.
- the pre-annealing and post-annealing may have different holding temperatures, and the post-annealing holding temperature may be higher or lower than the pre-annealing holding temperature. It is preferable that the retention times of the first stage annealing and the second stage annealing be 10% or more of the total retention time in the decarburization annealing, respectively.
- an annealing separator mainly composed of MgO to the surface of the steel sheet in an amount of 2.5 g/m 2 or more per side.
- "mainly composed of MgO” means that the content of MgO in the annealing separator is 60% or more in terms of solid content.
- the content of MgO in the annealing separator is preferably 80% or more in terms of solid content.
- MgO may be applied to the steel sheet in the form of a slurry, or may be dry applied by electrostatic coating. When applying the slurry, the slurry solution is preferably kept at a constant temperature of 5° C. or higher and 30° C. or lower in order to suppress an increase in viscosity.
- the slurry solution in order to keep the slurry concentration to be applied constant, it is preferable to separate the slurry solution into a mixing tank and a tank for application. By performing finish annealing thereafter, it is possible to develop secondary recrystallized grains and form a forsterite coating.
- the coil is then annealed in the up-end condition because the finish anneal is generally time consuming. It is preferable to prevent the outer winding of the up-end coil from unwinding by winding a band or the like around the coil before the final annealing.
- the temperature is preferably raised to 800°C or higher in order to complete secondary recrystallization, and in the case of forming a forsterite coating, the temperature is preferably raised to 1050°C or higher.
- the temperature is held at a temperature of 1050°C or higher and 1300°C or lower for 3 hours or more, and the temperature range of 1050°C or higher is partly or It is preferred to introduce an atmosphere containing all H2 .
- finish annealing it is useful to wash with water, brush, or pickle in order to remove the attached annealing separator. After that, flattening annealing is performed to correct the shape, which is effective for reducing iron loss.
- the coating is preferably a coating capable of imparting tension to the steel sheet to reduce iron loss.
- a coating liquid may be applied before flattening annealing, and baking may be performed by flattening annealing.
- a tension coating application method using a binder or a coating method in which inorganic substances are vapor-deposited on the steel sheet surface layer by physical vapor deposition or chemical vapor deposition is adopted, coating adhesion is excellent and iron loss is significantly reduced. preferable.
- Grain-oriented electrical steel sheet containing, in mass%, C: 0.092%, Si: 3.45%, Mn: 0.14%, Al: 0.022%, N: 0.007%, and S: 0.005%, with the balance being Fe and unavoidable impurities
- the slab for steel is reheated at a temperature of 1420°C and hot-rolled to produce a hot-rolled sheet with a thickness of 2.4 mm. removed. Then, the sheet was cold-rolled to a thickness of 0.50 mm, and further subjected to intermediate annealing at 1100°C for 100 seconds. In the intermediate annealing, the atmosphere was set to 60% H 2 +40% N 2 and the dew point was varied to adjust the amount of C in the steel sheet.
- the sheet was waited for the waiting time shown in Table 1, and then subjected to final cold rolling to finish the sheet to a thickness of 0.23 mm.
- pickling treatment was performed with a hydrochloric acid solution having an acid concentration of 5% at 70° C. for 3 seconds.
- Iron (III) chloride hexahydrate was previously added to the hydrochloric acid solution to contain 7% Fe ions.
- the iron content of the steel sheet was dissolved and the Fe ion concentration changed, so the concentration level was maintained by adding an aqueous hydrochloric acid solution to the hydrochloric acid solution.
- the first half is 835°C x 120 seconds, 50% H 2 + 50% N 2 , dew point 63°C (oxidizing 0.59), and the second half is 835°C x 20 seconds, 50% H 2 + 50% N 2 , dew point 30°C ( It was subjected to decarburization annealing with an oxidizing property of 0.09). Thereafter, after coating the surface of the steel sheet with an annealing separator mainly composed of MgO, the steel sheet was subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- a coating solution mainly composed of phosphate was applied, and the coating was baked at 850°C for 50 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the iron loss W 17/50 (magnetic flux density of 1.7 T, iron loss at 50 Hz excitation) of the obtained steel sheet was measured by the method described in JIS C2550-1 (2011).
- the amount of base iron C in the final product sheet is determined by the method described in JIS G1211-3: 2018 after removing the coating and film by pickling the obtained steel sheet with hydrochloric acid at a concentration of 5% at 90 ° C. for 180 seconds. analyzed.
- Table 1 the steel sheet after the final cold rolling was measured with an eddy current sensor type defect measuring device, and the presence or absence of defects such as cracks was evaluated by the number of defects per 1000 m. The results are also shown in Table 1.
- a slab for a grain-oriented electrical steel sheet is reheated at a temperature of 1230°C, hot rolled to produce a hot-rolled sheet with a thickness of 2.2 mm, and then hot-rolled sheet annealing is performed at 1100°C for 25 seconds to improve the surface of the steel sheet. Scale was removed by pickling. The hot-rolled sheet annealing was carried out under the condition that the atmosphere was 50% H 2 +50% N 2 and the dew point was 60°C.
- the final cold rolling was performed after waiting for 75 hours, and the sheet thickness was finished to 0.23 mm.
- pickling treatment was performed with a hydrochloric acid solution at 70° C. for 3 seconds at an acid concentration shown in Table 2.
- Iron (III) chloride hexahydrate was previously added to the hydrochloric acid solution to contain Fe ions at the concentration shown in Table 2.
- the iron content of the steel sheet was dissolved and the Fe ion concentration changed, so the concentration level was maintained by adding an aqueous hydrochloric acid solution to the hydrochloric acid solution.
- decarburization annealing was performed at 830°C for 90 seconds, 55% H 2 +45% N 2 , dew point 65°C.
- the steel sheet was subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- a coating liquid mainly composed of phosphate was applied, and the coating was baked at 840°C for 20 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the iron loss W 17/50 (magnetic flux density of 1.7 T, iron loss at 50 Hz excitation) of the obtained steel sheet was measured by the method described in JIS C2550-1 (2011).
- the amount of base iron C in the final product sheet was obtained by removing the coating and film by pickling the obtained steel sheet with hydrochloric acid at a concentration of 5% at 90 ° C. for 180 seconds, and then by the method described in JIS G1211-3: 2018. analyzed.
- Table 2 In this example, the steel sheet after the final cold rolling was measured with an eddy current sensor type defect measuring device, and the presence or absence of defects such as cracks was evaluated by the number of defects per 1000 m. The results are also shown in Table 2.
- the steel sheet was waited for 200 hours and then subjected to final cold rolling to finish the steel sheet to a thickness of 0.27 mm.
- the type of acid was changed as shown in Table 3, and pickling treatment was performed at 5% acid concentration at 65° C. for 5 seconds.
- Iron (III) chloride hexahydrate was previously added to the acid solution to contain Fe ions at the concentrations shown in Table 3. During the pickling, the iron content of the steel sheet was dissolved and the Fe ion concentration changed, so the concentration level was maintained by adding hydrochloric acid aqueous solution to the acid solution.
- decarburization annealing was performed at 850°C for 150 seconds in 50% H 2 +50% N 2 with a dew point of 60°C.
- the steel sheet was subjected to final annealing at 1200° C. for 10 hours in an H 2 atmosphere.
- a coating liquid mainly composed of phosphate was applied, and the coating was baked at 850°C for 20 seconds and the steel sheet was flattened. Flattening annealing was applied.
- the iron loss W 17/50 (magnetic flux density of 1.7 T, iron loss at 50 Hz excitation) of the obtained steel sheet was measured by the method described in JIS C2550-1 (2011).
- the amount of base iron C in the final product sheet was analyzed by the method described in JIS G1211-3: 2018 after removing the coating and film by pickling the obtained steel sheet with hydrochloric acid at a concentration of 5% at 90 ° C. for 180 seconds. .
- Table 3 In this experiment, the steel sheet after final cold rolling was measured with an eddy current sensor type defect measuring device, and the presence or absence of defects such as cracks was evaluated by the number of defects per 1000m. The results are also shown in Table 3.
- the method for producing a grain-oriented electrical steel sheet of the present invention it is possible to provide a grain-oriented electrical steel sheet suitable for the iron core material of transformers, and it is industrially highly useful.
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Abstract
Description
質量%で、C:0.060%、Si:3.08%、Mn:0.07%、Al:0.003%、N:0.003%およびS:0.003%を含有し、残部がFeおよび不可避的不純物からなる方向性電磁鋼板用スラブを、1210℃の温度で再加熱し、熱間圧延により2.4mm厚の熱延板を作製し、次いで950℃で10秒の熱延板焼鈍を施し、鋼板表面のスケールを酸洗にて除去した。次いで、冷間圧延により0.70mmの板厚とし、さらに1100℃で100秒の中間焼鈍を施した。中間焼鈍では、雰囲気を60%H2+40%N2とし、露点を種々変更することによって、この時点で脱炭を行って鋼板内のC量を種々に調節した。中間焼鈍後のC量を測定するため、この時点での小片サンプルを採取し、鋼板の表面から該鋼板の厚みの1/10の深さにおける層(以下、1/10層と示す)までを研削により除去し、1/10層から1/2層(板厚中心の層)までの平均C量をJIS G1211-3:2018記載の方法で評価した。
T≦-4000×A + 440かつ
T≦ 360
を満足する必要のあることを知見するに到った。
中間焼鈍後のC量が0.035%で待機時間が300時間の条件を満たす最終冷間圧延後の鋼板を、種々の酸濃度で60℃での塩酸溶液(処理液)を用いて酸洗を施した。さらに、塩酸溶液にあらかじめ塩化鉄(III)六水和物を添加することにより、種々の濃度のFeイオンを含有させた。実験中は、鋼板の鉄分が溶解してFeイオン濃度が変化するため、塩酸水溶液を追加して濃度レベルを維持した。その後、870℃×90秒、50%H2+50%N2、露点60℃の脱炭焼鈍を施した。その後、鋼板表面にMgO主体の焼鈍分離剤を塗布した後、1200℃で20時間、H2雰囲気下で保持する仕上焼鈍を施した。次いで、鋼板表面に残存した未反応の焼鈍分離剤を水洗にて除去した後、リン酸塩を主体としたコーティング液を塗布し、850℃で50秒のコーティング焼付と鋼板の平坦化を兼ねた平坦化焼鈍を施した。
すなわち、本発明の要旨構成は次のとおりである。
1.鋼素材を熱間圧延して熱延鋼板とし、前記熱延鋼板に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最終板厚を有する冷延鋼板とし、次いで前記冷延鋼板に脱炭焼鈍を施し、該鋼板の表面に焼鈍分離剤を塗布した後仕上焼鈍を施す、工程を含む、方向性電磁鋼板の製造方法において、
最終冷間圧延前に施される焼鈍後かつ前記最終冷間圧延前の鋼板における、該鋼板の表面からの深さが該鋼板の厚みの、1/10から1/2までの領域の、平均C量をA(質量%)とし、前記最終冷間圧延前に施される焼鈍の完了直後から前記最終冷間圧延開始直前までの時間をT(時間)とするとき、
T≦-4000×A + 440かつ
T≦ 360
を満たし、
前記最終冷間圧延後かつ前記脱炭焼鈍前に、酸濃度が1質量%以上20質量%以下およびFeイオン含有率が2質量%以上15質量%以下である処理液による、酸洗処理を行うことを特徴とする方向性電磁鋼板の製造方法。
前記前段焼鈍を雰囲気酸化性P(H2O)/P(H2)が0.3以上0.7以下の焼鈍雰囲気で行い、かつ
前記後段焼鈍を雰囲気酸化性P(H2O)/P(H2)が0.005以上0.2以下の焼鈍雰囲気にて行う、前記1または2に記載の方向性電磁鋼板の製造方法。
<鋼素材>
まず初めに、方向性電磁鋼板の鋼素材(鋼スラブ)の成分組成について、本発明では特に限定するものではないが、以下に好ましい成分組成の範囲を記載する。
Cは、0.10%を超えると、脱炭焼鈍後に磁気時効の起こらない50ppm以下に低減することが困難になるため、0.10%以下とすることが好ましい。一方、0.01%に満たないと、Cによる粒界強化効果が失われ、スラブに割れが生じるなど、操業性に支障がでる欠陥を引き起こす可能性がある。従って、Cは0.01%以上0.10%以下が好ましい。さらに好ましくは、0.03%以上であり、0.06%以下である。
Siは、鋼の比抵抗を高めて鉄損を改善させるために有用な元素であるが、2.0%未満では効果に乏しい。一方、5.0%を超えると、鋼の加工性が劣化して圧延が困難となる、虞がある。従って、Siは2.0%以上5.0%以下が好ましい。さらに好ましくは、3.0%以上であり、3.6%以下である。
Mnは、熱間加工性を良好にするために有用な元素であるが、0.01%未満であると効果に乏しいため、0.01%以上とすることが好ましい。一方、0.50%を超えると、製品板の磁束密度が低下するのため、0.50%以下が好ましい。さらに好ましくは0.03%以上であり、0.15%以下である。
すなわち、磁気特性を向上させる目的で、Ni:0%超1.50%以下、Cr:0%超0.50%以下、Cu:0%超0.50%以下、P:0%超0.50%以下、Sb:0%超0.50%以下、Sn:0%超0.50%以下、Bi:0%超0.50%以下、Mo:0%超0.50%以下、B:0ppm超25ppm以下、Nb:0%超0.020%以下、V:0%超0.010%以下、Zr:0%超0.10%以下、Co:0%超0.050%以下、Pb:0%超0.0100%以下、As:0%超0.0200%以下、Zn:0%超0.020%以下、W:0%超0.0100%以下、Ge:0%超0.0050%以下、およびGa:0%超0.0050%以下からなる群より選択される一種または2種以上を添加できる。それぞれ添加量が上限量を超えると、二次再結晶粒の発達が抑制され磁気特性が劣化する、おそれがある。
C:0.01%以上0.10%以下、
Si:2.0%以上5.0%以下、
Mn:0.01%以上0.50%以下、ならびに
α群:Al:0.01%以上0.04%以下とN:0.003%以上0.010%以下、および
β群:SもしくはSeのいずれか1種または2種を合計0.005%以上0.100%以下
のいずれか一方または両方
を含有し、残部がFeおよび不可避的不純物からなる成分組成を有することができる。
また、鋼素材は、
C:0.01%以上0.10%以下、
Si:2.0%以上5.0%以下、
Mn:0.01%以上0.50%以下、
Al:0.010%以下、
N:0.0060%以下、ならびに
SおよびSeのうちいずれか1種または2種を合計で0.010%以下
を含有し、残部がFeおよび不可避的不純物からなる成分組成を有することができる。
上記の鋼素材は、さらに、
Ni:0%超1.50%以下、
Cr:0%超0.50%以下、
Cu:0%超0.50%以下、
P:0%超0.50%以下、
Sb:0%超0.50%以下、
Sn:0%超0.50%以下、
Bi:0%超0.50%以下、
Mo:0%超0.50%以下、
B:0ppm超25ppm以下、
Nb:0%超0.020%以下、
V:0%超0.010%以下、
Zr:0%超0.10%以下、
Co:0%超0.050%以下、
Pb:0%超0.0100%以下、
As:0%超0.0200%以下、
Zn:0%超0.020%以下、
W:0%超0.0100%以下、
Ge:0%超0.0050%以下、および
Ga:0%超0.0050%以下
からなる群より選択される一種または2種以上を含有してもよい。
上記成分を有する溶鋼は、通常の造塊法、連続鋳造法でスラブを製造してもよいし、100mm以下の厚さの薄鋳片を直接鋳造法で製造してもよい。これら鋼素材としてのスラブや薄鋳片は、通常の方法で加熱された後熱間圧延するが、鋳造後加熱せずに直ちに熱間圧延を施してもよい。上記の加熱温度は、インヒビタを利用する成分系の場合、1300℃以上で加熱して、インヒビタ成分を固溶させることが好ましい。一方、インヒビタを利用しない場合は、1300℃以下で加熱することがコストの観点からは好ましい。
T≦-4000×A + 440かつ
T≦ 360
を満足する必要がある。
処理液の酸は、特に限定されず、リン酸、塩酸、硫酸または硝酸が挙げられる。酸は単独でも、2種以上であってもよく、水溶液の形態で使用することが好ましい。
処理液のFeイオン含有率は、処理液に鉄化合物を添加することにより調整することができる。鉄化合物としては、塩化鉄(III)六水和物、リン酸鉄(III)等が挙げられる。鉄化合物は単独でも、2種以上であってもよい。
処理中に鋼板の鉄分が溶解して、処理液のFe濃度が変動するが、酸の水溶液を添加してFe濃度を一定に維持することが好ましい。酸としては、処理の酸として例示した酸を使用することができる。
MgOはスラリー状で鋼板に塗布されるほか、静電塗装による乾式塗布でもよい。スラリー塗布の際は、粘度上昇を抑制するために、スラリー溶液は5℃以上30℃以下で一定の温度で保持されることが好ましい。また塗布するスラリー濃度を一定に維持するために、スラリー溶液は調合用のタンクと、塗布に供するタンクとを分けることが好ましい。その後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共に、フォルステライト被膜を形成させることが可能である。
Claims (3)
- 鋼素材を熱間圧延して熱延鋼板とし、前記熱延鋼板に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最終板厚を有する冷延鋼板とし、次いで前記冷延鋼板に脱炭焼鈍を施し、該鋼板の表面に焼鈍分離剤を塗布した後仕上焼鈍を施す、工程を含む、方向性電磁鋼板の製造方法において、
最終冷間圧延前に施される焼鈍後かつ前記最終冷間圧延前の鋼板における、該鋼板の表面からの深さが該鋼板の厚みの、1/10から1/2までの領域の、平均C量をA(質量%)とし、前記最終冷間圧延前に施される焼鈍の完了直後から前記最終冷間圧延開始直前までの時間をT(時間)とするとき、
T≦-4000×A + 440かつ
T≦ 360
を満たし、
前記最終冷間圧延後かつ前記脱炭焼鈍前に、酸濃度が1質量%以上20質量%以下およびFeイオン含有率が2質量%以上15質量%以下である処理液による、酸洗処理を行う方向性電磁鋼板の製造方法。 - 前記酸洗処理にて使用する酸が、リン酸、塩酸、硫酸および硝酸からなる群より選択される、請求項1に記載の方向性電磁鋼板の製造方法。
- 前記脱炭焼鈍が、前段焼鈍と後段焼鈍とに分かれ、
前記前段焼鈍を雰囲気酸化性P(H2O)/P(H2)が0.3以上0.7以下の焼鈍雰囲気にて行い、かつ
前記後段焼鈍を雰囲気酸化性P(H2O)/P(H2)が0.005以上0.2以下の焼鈍雰囲気にて行う、請求項1または2に記載の方向性電磁鋼板の製造方法。
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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 |
JP2007169762A (ja) * | 2005-12-26 | 2007-07-05 | Jfe Steel Kk | 低鉄損方向性電磁鋼板の製造方法 |
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JPS5113469B2 (ja) | 1972-10-13 | 1976-04-28 | ||
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 |
JP2007169762A (ja) * | 2005-12-26 | 2007-07-05 | Jfe Steel Kk | 低鉄損方向性電磁鋼板の製造方法 |
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