WO2025005167A1 - 方向性電磁鋼板 - Google Patents
方向性電磁鋼板 Download PDFInfo
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- WO2025005167A1 WO2025005167A1 PCT/JP2024/023282 JP2024023282W WO2025005167A1 WO 2025005167 A1 WO2025005167 A1 WO 2025005167A1 JP 2024023282 W JP2024023282 W JP 2024023282W WO 2025005167 A1 WO2025005167 A1 WO 2025005167A1
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Definitions
- the present invention relates to a grain-oriented electrical steel sheet. This application claims priority based on Japanese Patent Application No. 2023-106860, filed on June 29, 2023, the contents of which are incorporated herein by reference.
- Grain-oriented electrical steel sheet contains silicon, and the crystal orientation of its crystal grains is concentrated near the Goss orientation (cubic ⁇ 110 ⁇ 001>), with the ⁇ 001> orientation, which is the axis of easy magnetization, being nearly aligned with the rolling direction in the steel sheet manufacturing process.
- Such grain-oriented electrical steel sheet is extremely useful as a material for the iron cores of transformers, etc.
- One of the important magnetic properties of grain-oriented electrical steel sheet is magnetic flux density.
- Magnetic flux density B8 is generally used as an index of magnetic flux density.
- Magnetic flux density B8 is the value of the magnetic flux density of a magnetized grain-oriented electrical steel sheet when a magnetizing force of 800 A/m is applied in the rolling direction.
- a grain-oriented electrical steel sheet with a higher magnetic flux density B8 value is more easily magnetized with a certain magnetizing force and has a higher magnetic flux density, making it suitable for small, highly efficient transformers.
- Patent Documents 1 and 2 disclose a method for advancing secondary recrystallization in the finish annealing process by applying a temperature gradient to the steel sheet in the tip region of the secondary recrystallized grains that are encroaching on the primary recrystallized grains.
- secondary recrystallization progresses when the steel sheet is wound into a coil.
- the secondary recrystallized grains grow when the steel sheet has a curvature.
- the secondary recrystallized grains grow while maintaining the linearity of the crystal orientation. Therefore, the larger the secondary recrystallized grains grow, the greater the deviation from the ideal Goss orientation at the tip region of the secondary recrystallized grain growth due to the curvature of the coil.
- Deviation angle ⁇ is the angle between the ⁇ 001> direction of the crystal projected onto the rolling surface when viewed from the rolling surface normal direction Z and the rolling direction L.
- Deviation angle ⁇ is the angle between the ⁇ 001> direction of the crystal projected onto the L cross section (cross section whose normal is the rolling direction perpendicular to the rolling) when viewed from the rolling perpendicular direction C (plate width direction) and the rolling direction L.
- Deviation angle ⁇ is the angle between the ⁇ 110> direction of the crystal projected onto the C cross section (cross section whose normal is the rolling direction) when viewed from the rolling direction L and the rolling surface normal direction Z.
- misalignment angle ⁇ affects magnetostriction.
- Magnetostriction is a phenomenon in which a magnetic body changes shape when a magnetic field is applied. In grain-oriented electrical steel sheets used in transformers, etc., magnetostriction causes vibration and noise, so small magnetostriction is required.
- Patent Documents 3 to 5 disclose controlling the misalignment angle ⁇ .
- the present invention has been made in consideration of the above problems. It is an object of the present invention to provide a grain-oriented electrical steel sheet that is excellent in magnetic flux density and magnetostriction characteristics. Specifically, it is an object of the present invention to provide a grain-oriented electrical steel sheet that is excellent in both magnetic flux density and magnetostriction characteristics, even when a technology that imparts a temperature gradient to the steel sheet during secondary recrystallization is applied.
- the gist of the present invention is as follows:
- a grain-oriented electrical steel sheet is The deviation angle from the ideal Goss orientation with the normal direction Z of the rolling surface as the rotation axis is defined as ⁇ ,
- the deviation angle from the ideal Goss orientation with the direction perpendicular to the rolling direction C as the rotation axis is defined as ⁇ ,
- the deviation angle from the ideal Goss orientation with the rolling direction L as the rotation axis is defined as ⁇ ,
- the deviation angle of the crystal orientation measured at one measurement point on the plate surface is represented as ( ⁇ ⁇ ⁇ ),
- ave ⁇ L When the average value of the angle deviation ⁇ obtained at a plurality of measurement points spaced at intervals of 1 mm along the rolling direction L is defined as ave ⁇ L ,
- the ave ⁇ L satisfies ave ⁇ L ⁇ 3.5°
- FIG. 2 is a diagram showing an example of using spot current heating as a local rapid heating method, and is a schematic diagram showing an example of the arrangement of local heat affected regions in a decarburized annealed steel sheet.
- FIG. 2 is a schematic diagram showing the distribution of Goss-oriented grains in a decarburized annealed steel sheet.
- the grain-oriented electrical steel sheet (base steel sheet) has The deviation angles of the crystal orientations measured at two adjacent measurement points on the plate surface, spaced 1 mm apart, are represented as ( ⁇ 1 ⁇ 1 ⁇ 1 ) and ( ⁇ 2 ⁇ 2 ⁇ 2 ), The midpoint between two measurement points that satisfy [( ⁇ 2 - ⁇ 1 ) 2 + ( ⁇ 2 - ⁇ 1 ) 2 + ( ⁇ 2 - ⁇ 1 ) 2 ] 1/2 ⁇ 1.0° is defined as the grain boundary GB, The grain size in the rolling direction L determined based on the grain boundary GB is defined as DL in mm, When the grain sizes D L obtained along the rolling direction L are arranged in ascending order, the grain size that is 10% by number from the largest grains is defined as D L 10 in units of mm, The above D L 10 satisfies D L 10 ⁇ 100 ⁇ 15 ⁇ ave ⁇ L.
- the grain-oriented electrical steel sheet (base steel sheet) has The grain size in the direction perpendicular to the rolling direction C obtained based on the grain boundary GB is defined as DC in mm.
- the average value of the grain diameter D C measured along the direction perpendicular to the rolling direction C is defined as aveD C .
- the above aveD C satisfies aveD C ⁇ 50.
- the angle deviation ⁇ is defined by the deviation angles ⁇ and ⁇ .
- the angle deviation ⁇ is often evaluated by three components, the deviation angles ⁇ , ⁇ , and ⁇ .
- the angle deviation ⁇ is defined by two components, the deviation angles ⁇ and ⁇ , excluding the deviation angle ⁇ , which has little effect on the magnetic flux density and magnetostriction characteristics. If the above conditions are satisfied using this angle deviation ⁇ , the above effects can be obtained.
- the grain boundaries and grain sizes can be determined based on the three components, the deviation angles ⁇ , ⁇ , and ⁇ .
- the ave ⁇ L being 3.5° or less means that the angle deviation ⁇ is small on average at each measurement point along the rolling direction L. That is, it means that the angle deviation between the rolling direction L and the magnetization easy axis direction is small.
- the magnetic properties, particularly the magnetic flux density are preferably improved.
- the ave ⁇ L is preferably 3.2° or less, more preferably 3.0° or less, and more preferably 2.7° or less.
- the ave ⁇ L may be 0.5° or more, or 1.0° or more.
- D L 10 is (100-15 ⁇ ave ⁇ L ) mm or less. If the crystal grains do not grow coarsely in the rolling direction L, the increase in the above-mentioned shift angle, particularly the shift angle ⁇ , can be suppressed. If the increase in the shift angle ⁇ is suppressed, the decrease in magnetic flux density and the increase in magnetostriction are also suppressed.
- D L 10 satisfies the above conditions, the magnetic flux density and magnetostriction characteristics are preferably improved. It is more preferable that D L 10 is (90-15 ⁇ ave ⁇ L ) mm or less, and more preferably (80-15 ⁇ ave ⁇ L ) mm or less. On the other hand, since the smaller the value of D L 10, the more preferable, the lower limit is not particularly limited. For example, D L 10 may be 5 mm or more, or 10 mm or more.
- the aveD C being 50 mm or more indicates that the shape of the crystal grains is elongated in the direction C perpendicular to the rolling direction.
- the grain-oriented electrical steel sheet according to the present embodiment is based on the premise that a technology of applying a temperature gradient to the steel sheet during secondary recrystallization is applied. Therefore, the secondary recrystallized grains tend to grow coarsely. However, in the present embodiment, as described above, the grains are suppressed from growing coarsely in the rolling direction L. On the other hand, in the present embodiment, the grains are allowed to grow coarsely in the direction C perpendicular to the rolling direction.
- the grain-oriented electrical steel sheet according to the present embodiment applies a technology of applying a temperature gradient to the steel sheet during secondary recrystallization, the secondary recrystallized grains tend to grow coarsely, and the aveD C is 50 mm or more.
- the aveD C is preferably 80 mm or more, more preferably 100 mm or more, and more preferably 200 mm or more.
- the upper limit of the aveD C is not particularly limited.
- the grain size of the grains in the direction C perpendicular to the rolling direction may be the coil width (for example, width 1000 mm).
- the aveD C may be equal to or less than 800 mm, or may be equal to or less than 500 mm.
- the above-mentioned deviation angles ⁇ , ⁇ , ⁇ , etc. can be measured by setting a measurement line including at least 500 measurement points at 1 mm intervals on the rolled surface to measure the crystal orientation.
- the crystal orientation can be measured by X-ray diffraction method (Laue method).
- the Laue method is a method in which an X-ray beam is irradiated onto a steel sheet and the transmitted or reflected diffraction spots are analyzed. By analyzing the diffraction spots, the crystal orientation at the location where the X-ray beam was irradiated can be identified. By changing the irradiation position and analyzing the diffraction spots at multiple locations, the crystal orientation distribution at each irradiation position can be measured.
- the Laue method is a method suitable for measuring the crystal orientation of a metal structure with coarse crystal grains.
- the crystal orientation is measured at 1 mm intervals on the rolled surface, and the above-mentioned deviation angle ⁇ , deviation angle ⁇ , deviation angle ⁇ , etc. are specified for each measurement point. Based on the deviation angle at each specified measurement point, the angle deviation ⁇ , ave ⁇ L , grain boundary GB, grain size D L , D L 10, grain size D C , and aveD C may be obtained.
- D L 10 the grain size that is 10% of the grains in terms of number may be obtained by arranging the grains with a grain size D L of 2 mm or more in descending order.
- aveD C the average grain size may be obtained based on the grains with a grain size D C of 2 mm or more.
- 0.5 mm may be added to the grain size of each of the two grains.
- the grain-oriented electrical steel sheet according to this embodiment has a chemical composition that contains, by mass fraction, 2.0% to 7.0% Si, with the remainder being Fe and impurities.
- this grain-oriented electrical steel sheet may contain publicly known optional elements in place of a portion of Fe in order to improve the magnetic properties.
- the lower limit may be 0%.
- the upper limit for the optional elements may be set to a range in which no significant decrease in magnetic flux density or iron loss occurs. The approximate upper limit for each optional element is listed below.
- the grain-oriented electrical steel sheet (base steel sheet) has a chemical composition, in mass%, of: Si: 2.0 to 7.0%, C: 0 to 0.0050%, Mn: 0 to 1.0%, S and Se: 0 to 0.0150% in total, Al: 0-0.0650%, N: 0 to 0.0050%, Nb, V, Mo, Ta, and W: 0 to 0.050% in total; Cu: 0 to 0.40%, Bi: 0 to 0.010%, B: 0 to 0.080%, P: 0-0.50%, Ti: 0 to 0.0150%, Sn: 0 to 0.10%, Sb: 0 to 0.10%, Cr: 0 to 0.30%, Ni: 0-1.0%, and the remainder being Fe and impurities.
- Si 2.0-7.0%
- Silicon (Si) is a basic element for the base steel sheet. If the Si content is less than 2.0%, the eddy current loss cannot be sufficiently reduced, and good magnetic properties cannot be obtained.
- the Si content of the steel plate is 2.0% or more.
- the Si content is preferably 2.50% or more, and more preferably 3.0% or more.
- the Si content is 7.0%, If the Si content exceeds 7.0%, the steel sheet becomes brittle and the sheet passing property during production is significantly deteriorated, so the Si content of the base steel sheet is set to 7.0% or less.
- the Si content is preferably 4.50% or less. More preferably, it is 4.0% or less.
- C is an optional element for base steel plate.
- C is contained in the steel slab, but if excessive C remains in the base steel plate after final annealing, good core loss characteristics cannot be obtained. Therefore, the C content of the base steel sheet may be 0.0050% or less, preferably 0.0040% or less, and more preferably 0.0030% or less.
- the lower limit of the C content of the base steel sheet is not particularly limited and may be 0%. However, since it is not industrially easy to make the C content 0%, may be more than 0%, or may be 0.00010% or more.
- Mn 0 to 1.0%
- Mn manganese
- Mn is a selective element for the base steel sheet. Mn is contained in the steel slab, but if it is contained in excess, the steel undergoes phase transformation during secondary recrystallization annealing, secondary recrystallization does not proceed sufficiently, and good magnetic properties may not be obtained. Therefore, the Mn content of the base steel sheet may be 1.0% or less. The Mn content is preferably 0.50% or less, more preferably 0.20% or less.
- the lower limit of the Mn content of the base steel sheet is not particularly limited and may be 0%. However, since Mn forms MnS and MnSe and has the effect of acting as an inhibitor during secondary recrystallization, the Mn content may be more than 0% or may be 0.00010% or more.
- S and Se are selective elements for the base steel sheet.
- S and Se are contained in the steel slab, but if S and Se remain in excess in the base steel sheet after finish annealing, it may adversely affect the magnetic properties. Therefore, the total content of S and Se in the base steel sheet may be 0.0150% or less.
- the total content of S and Se is preferably 0.010% or less, more preferably 0.0050% or less.
- the lower limit of the total content of S and Se in the base steel sheet is not particularly limited and may be 0%. However, since S and Se form MnS and MnSe and have the effect of an inhibitor during secondary recrystallization, the total content of S and Se may be more than 0% or may be 0.00010% or more.
- Al is an optional element for base steel sheets. Al is contained in steel slabs, but if excessive Al remains in the base steel sheet after final annealing, it can adversely affect the magnetic properties. Therefore, the Al content of the base steel sheet may be 0.0650% or less. The Al content is preferably 0.040% or less, and more preferably 0.035% or less. The lower limit of the Al content of the base steel sheet is not particularly limited and may be 0%. However, since Al forms AlN and has an effect as an inhibitor during secondary recrystallization, the Al content is The amount of Al may be more than 0% or may be 0.00010% or more. Note that the above content of Al is acid-soluble Al (sol. Al).
- N is an optional element for base steel sheets.
- N is contained in the steel slab, but if excessive N remains in the base steel sheet after final annealing, it can adversely affect the magnetic properties. Therefore, the N content of the base steel sheet may be 0.0050% or less.
- the N content is preferably 0.0040% or less, and more preferably 0.0030% or less.
- the lower limit of the N content of the base steel sheet is not particularly limited and may be 0%. However, since N forms AlN and has an effect as an inhibitor during secondary recrystallization, the N content is The amount may be greater than 0% or may be 0.00010% or greater.
- Nb, V, Mo, Ta, and W are optional elements for the base steel plate. If an excessive amount of Nb group elements (one or more of Nb, V, Mo, Ta, and W) remains in the base steel plate, it may adversely affect the magnetic properties. Therefore, the total content of Nb, V, Mo, Ta, and W in the base steel plate may be 0.050% or less.
- the Nb group elements are preferably 0.030% or less, preferably 0.020% or less, and more preferably 0.010% or less.
- the total content of Nb, V, Mo, Ta, and W in the base steel plate is not particularly limited and may be 0%. However, since Nb, V, Mo, Ta, or W forms carbides, nitrides, or carbonitrides and has the effect of acting as an inhibitor during secondary recrystallization, the total content of Nb, V, Mo, Ta, and W may be more than 0% or may be 0.003% or more.
- Cu is an optional element for the base steel sheet. If the Cu content exceeds 0.40%, the steel sheet may become embrittled during hot rolling. Therefore, the Cu content of the base steel sheet is The Cu content is preferably 0.30% or less, and more preferably 0.10% or less. On the other hand, the lower limit of the Cu content is not particularly limited. However, since Cu has the effect of increasing the concentration of the Goss orientation and improving the magnetic properties, the Cu content may be more than 0%, and is set to 0.010% or more. Good too.
- Bi 0 ⁇ 0.010%
- Bi bismuth
- the Bi content of the base steel sheet may be 0.010% or less.
- the Bi content is preferably 0.0050% or less, and more preferably 0.0050% or less.
- the Bi content is 0.0020% or less, and more preferably 0.0010% or less.
- the lower limit of the Bi content is not particularly limited and may be 0%. However, Bi improves the magnetic flux density. Therefore, the Bi content may be set to more than 0% or to 0.00050% or more.
- B 0-0.080%
- B (boron) is an optional element for the base steel sheet. If the B content exceeds 0.080%, the variation (standard deviation) of the magnetic flux density may become large. Therefore, the B content is set to 0.
- the Bi content is preferably 0.070% or less, and more preferably 0.060% or less.
- the lower limit of the B content is not particularly limited, and is 0%. However, since B forms nitrides and has an effect as an inhibitor during secondary recrystallization, the B content may be more than 0% or may be 0.00050% or more. .
- P 0 to 0.50%
- P (phosphorus) is a selective element for the base steel sheet. If the P content exceeds 0.50%, the workability of the steel sheet may be significantly reduced. Therefore, the P content of the base steel sheet may be 0.50% or less.
- the P content is preferably 0.30% or less, more preferably 0.10% or less.
- the lower limit of the P content is not particularly limited and may be 0%. However, since P has the effect of improving the texture and improving the magnetic properties of the steel sheet, the P content may be more than 0% or may be 0.0020% or more.
- Ti is an optional element for the base steel plate. If the Ti content exceeds 0.0150%, the magnetic properties may be significantly reduced. Therefore, the Ti content of the base steel plate is set to 0.0150% or less. % or less. The Ti content is preferably 0.0130% or less, and more preferably 0.010% or less. On the other hand, the lower limit of the Ti content is not particularly limited, and is not limited to 0%. However, since Ti forms carbides, nitrides, and carbonitrides and has the effect of acting as an inhibitor during secondary recrystallization, the Ti content may be more than 0%, and may be less than 0.0020%. % or more.
- Sn 0-0.10%
- Sn (tin) is an optional element for the base steel sheet. If the Sn content exceeds 0.10%, the secondary recrystallization becomes unstable and may adversely affect the magnetic properties.
- the Sn content of the steel sheet may be 0.10% or less.
- the Sn content is preferably 0.090% or less, and more preferably 0.080% or less.
- the lower limit of the Sn content is However, since Sn has the effect of increasing the concentration of the Goss orientation and improving the magnetic properties, the Sn content may be more than 0%, and may be 0% or less. It may be 0.0050% or more.
- Sb 0-0.10%
- Sb antimony
- the Sb content of the base steel sheet is set to 0.10% or less.
- the Sb content is preferably 0.090% or less, and more preferably 0.080% or less.
- the lower limit of the Sb content is not particularly limited, and is not limited to 0%. However, since Sb functions as an inhibitor and has the effect of stabilizing secondary recrystallization, the Sb content may be more than 0% or may be 0.010% or more.
- Cr 0-0.30% Cr (chromium) is an optional element for the base steel plate. If the Cr content exceeds 0.30%, Cr oxides are formed, which may adversely affect the magnetic properties.
- the Cr content may be 0.30% or less.
- the Cr content is preferably 0.20% or less, and more preferably 0.10% or less.
- the lower limit of the Cr content is particularly However, since Cr has the effect of increasing the concentration of Goss orientation and improving magnetic properties, the Cr content may be more than 0%, and may be 0.010 % or more.
- Ni 0 to 1.0%
- Ni (nickel) is an optional element for the base steel plate. If the Ni content exceeds 1.0%, secondary recrystallization may become unstable. Therefore, the Ni content of the base steel plate may be 1.0% or less.
- the Ni content is preferably 0.20% or less, more preferably 0.10% or less.
- the lower limit of the Ni content is not particularly limited and may be 0%. However, since Ni has the effect of increasing electrical resistance and reducing iron loss, the Ni content may be more than 0% or may be 0.010% or more.
- the base steel sheet of the grain-oriented electrical steel sheet according to this embodiment may contain impurities.
- impurities refer to substances that are mixed in from raw materials such as ore or scrap during industrial production of steel, or from the production environment, etc.
- the chemical composition of the above-mentioned base steel plate may be measured by a general analytical method. For example, it may be measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry). Acid-soluble Al may be measured by ICP-AES using the filtrate after thermally decomposing the sample with acid. C and S may be measured using the combustion-infrared absorption method, N using the inert gas fusion-thermal conductivity method, and O using the inert gas fusion-non-dispersive infrared absorption method.
- ICP-AES Inductively Coupled Plasma-Atomic Emission Spectrometry
- Acid-soluble Al may be measured by ICP-AES using the filtrate after thermally decomposing the sample with acid.
- C and S may be measured using the combustion-infrared absorption method, N using the inert gas fusion-thermal conductivity method, and O using the inert gas fusion-non-dispersive infrared absorption
- the above chemical composition is that of the base steel sheet. If the grain-oriented electrical steel sheet to be used as the measurement sample has an insulating coating on its surface, the coating is removed using the method described below before measuring the chemical composition.
- the insulating coating can be removed by immersing the grain-oriented electrical steel sheet having the coating in a high-temperature alkaline solution.
- the insulating coating can be removed from the grain-oriented electrical steel sheet by immersing the sheet in an aqueous sodium hydroxide solution containing 30 to 50 mass % NaOH and 50 to 70 mass % H 2 O at 80 to 90° C. for 5 to 10 minutes, followed by rinsing with water and drying.
- the time for immersion in the aqueous sodium hydroxide solution can be changed depending on the thickness of the insulating coating.
- the electrical steel sheet from which the insulating coating has been removed using the above method may be immersed in hot hydrochloric acid.
- the preferred concentration of hydrochloric acid for removing the forsterite coating to be dissolved is determined in advance, and the forsterite coating can be removed by immersing the sheet in hydrochloric acid of this concentration (e.g. 30-40% by mass hydrochloric acid) at 80-90°C for 1-5 minutes, followed by rinsing with water and drying.
- different treatment solutions are used to remove each coating, such as using an alkaline solution to remove the insulating coating and hydrochloric acid to remove the forsterite coating.
- a grain-oriented electrical steel sheet with excellent quality can be obtained by performing local rapid heating on a cold-rolled steel sheet to form a localized heated region, controlling the annealing conditions of the primary annealing (decarburization annealing), and controlling the annealing conditions of the secondary annealing (finish annealing).
- the locally heated region formed before the primary annealing is located locally on the surface of the steel plate.
- the crystalline structure of this locally heated region consists of one or both of a recrystallized structure and a recovered structure at the end of the local rapid heating.
- the crystalline structure of the non-rapidly heated parts of the steel plate surface other than the locally heated region consists of a cold worked structure that remains as it is cold rolled.
- the above-mentioned localized rapid heating has a heating rate of 500°C/sec or more, preferably 2000°C/sec or more, and more preferably 10000°C/sec or more.
- the frequency of coarse Goss orientation grains in the localized heating affected area is greater than that obtained by normal rapid heating of the entire plate. This characteristic is thought to be due to the fact that the peripheral area of the locally heated area is a processed structure that retains a lot of distortion. Specifically, when localized rapid heating is performed, the practical Goss orientation grains generated in the locally heated area preferentially encroach on the peripheral unrecrystallized area that retains a lot of distortion during the primary annealing, and grow in diameter. However, when the entire steel plate is heated, the generation and growth of recrystallized grains occurs uniformly within the steel plate, so it is thought that the above-mentioned enlargement does not occur.
- secondary annealing is then performed.
- secondary annealing secondary recrystallization is promoted while applying a temperature gradient to the steel sheet.
- the Goss-oriented grains formed in the local heat-affected zone grow preferentially during secondary annealing.
- Many Goss-oriented grains are formed in the local heat-affected zone, and among these are Goss-oriented grains that are close to the ideal Goss orientation, with particularly small angle deviations ⁇ and ⁇ , and have large crystal grain sizes after primary annealing, and these Goss-oriented grains grow preferentially during secondary recrystallization.
- Goss orientation grains that serve as the nuclei for secondary recrystallization are supplied to the local heat affected region, there is no need to form Goss orientation grains in the primary annealing in the matrix parts other than the local heat affected region, i.e., the local heat unaffected region. Therefore, as the heat treatment conditions for the primary annealing, a slow heating condition with a low heating rate may be adopted, which forms many corresponding orientation grains with the ⁇ 111 ⁇ 112> and ⁇ 411 ⁇ 148> orientations that are easily eroded in the local heat unaffected region.
- the heating rate for the primary annealing to 300°C/sec or less, many Goss orientation grains with large crystal grain size and close to the ideal Goss orientation are formed in the local heat affected region, while almost no Goss orientation grains are formed in the local heat unaffected region, and conversely, many corresponding orientation grains can be formed.
- secondary recrystallization is advanced by applying a temperature gradient to the steel sheet in the tip region of the secondary recrystallized grains that are encroaching on the primary recrystallized grains during secondary annealing.
- secondary recrystallized grains are grown using a temperature gradient, secondary recrystallized grains with an orientation close to the ideal Goss orientation are generated from the part of the steel sheet that reaches the secondary recrystallization start state early, and these secondary recrystallized grains grow preferentially due to the temperature gradient.
- the degree of accumulation in the Goss orientation is preferably increased.
- the direction in which the above temperature gradient is applied may be the direction C perpendicular to the rolling direction.
- the secondary recrystallized grains when the secondary recrystallized grains are grown using a temperature gradient, the secondary recrystallized grains become excessively large, and the deterioration of the slip angle ⁇ due to the coil set cannot be avoided.
- the secondary recrystallized Goss orientation grains tend to grow on the low temperature side of the steel sheet (rolling vertical direction C), but at that time, the secondary recrystallized grains also grow in the rolling direction L. Therefore, the crystal grain size D L in the rolling direction also becomes large.
- the above-mentioned local rapid heating can increase the frequency of the secondary recrystallized grains close to the ideal Goss orientation, so that the increase in the crystal grain size D L in the rolling direction can be suppressed, and the deterioration of the slip angle ⁇ due to the coil set can be suppressed.
- a steel sheet having a better magnetic flux density and magnetostriction characteristics than the conventional steel sheet can be obtained.
- secondary recrystallized grains having an orientation close to the ideal Goss orientation are preferentially generated, so that the deterioration of the misalignment angle ⁇ can be suppressed, and thus a steel sheet having a higher magnetic flux density than conventional steel sheets can be obtained.
- spot current heating by electrical resistance heating is described below.
- spot current heating spot electrodes are pressed against both sides of a steel sheet, and current is passed between the spot electrodes to spot current heat the electrode holding portion of the steel sheet.
- a steel having the composition shown in Table 1 was used, and a cold-rolled steel sheet with a sheet thickness of 0.22 mm was obtained by hot rolling and cold rolling. This steel sheet was subjected to spot current heating.
- the spot current heating was performed using a copper electrode with a diameter of 3 mm, under the following conditions: current of 5.0 kA or less, which is a range in which the steel sheet surface does not melt, current time of 20 milliseconds to 80 milliseconds, electrode pressure of 50 kgf to 150 kgf, and electrode holding time after current application of 0.2 seconds.
- Spot current heating was performed on the surface of the cold-rolled steel sheet at a position 10 mm from the end of the cold-rolled steel sheet in the direction perpendicular to the rolling direction, with a pitch of 20 mm in the rolling direction, to form a localized heating region.
- This cold-rolled steel sheet was subjected to decarburization annealing (primary annealing). In the decarburization annealing, the cold-rolled steel sheet was heated at a heating rate of 20°C/sec and held at 830°C for 90 seconds.
- Figure 1 shows an example of the arrangement of local heat affected areas in a decarburized annealed steel sheet manufactured under the above conditions.
- the decarburized annealed steel sheet 1 the local heat affected areas 2, the rolling direction 21, and the width direction (direction perpendicular to the rolling direction) 22 are shown diagrammatically.
- FIG. 1 is a schematic diagram showing the distribution of Goss orientation grains in the decarburized annealed steel sheet manufactured under the above conditions.
- the current-carrying electrode used for spot current heating is circular, and its diameter is preferably 0.5 mm ⁇ to 10 mm ⁇ , and more preferably 1 mm ⁇ to 5 mm ⁇ , in terms of circle equivalent diameter. Note that, although a circular current-carrying electrode was used in the above, it is sufficient to locally increase the heating rate of the cold-rolled steel sheet, form Goss-oriented grains in this region, and allow the grains to grow; the electrode shape may be other shapes, for example, elliptical or linear.
- the decarburized annealed steel sheet 1 manufactured under the above conditions contains Goss orientation grains 14 as well as coarse Goss orientation grains 15.
- the region containing the coarse Goss orientation grains 15 corresponds to the local heat affected region 2.
- Figure 2 shows a schematic of the local heat affected region boundary 4 and the local heat affected region boundary 5, it is not easy to distinguish these boundaries by observing the structure.
- the region containing the coarse Goss orientation grains 15 can be considered to be the local heat affected region 2.
- the above decarburized annealed steel sheets were further nitrided, coated with an annealing separator mainly composed of MgO, and then subjected to secondary annealing.
- the secondary annealing conditions were: hydrogen/nitrogen atmosphere, heating rate: 15°C/hr (°C/hr), holding: 1200°C-20hr (hr).
- a temperature gradient of 5°C/cm was applied in the direction perpendicular to the rolling direction at the boundary between the primary and secondary recrystallization regions in the steel sheet.
- the obtained steel plate was subjected to macro-etching to reveal the grain boundaries.
- macro-etching was observed at the locations corresponding to the local heat affected areas, it was found that in some cases multiple secondary recrystallized grains had grown from the locations corresponding to the local heat affected areas, and in other cases secondary recrystallized grains had spread from the center of the locations corresponding to the local heat affected areas.
- minute grains of 2 mm or less were sometimes observed as traces of the local heat affected areas, but in other cases they were not.
- the secondary recrystallized macrostructure may change slightly depending on the local heating conditions, the degree of accumulation in the Goss orientation was increased compared to when local heat treatment was not performed.
- the crystal orientation of the obtained steel sheet was measured by the Laue method described above.
- the obtained steel sheet had an ave ⁇ L of 3.5° or less, a DL 10 of (100-15 ⁇ ave ⁇ L ) mm or less, and an aveD C of 50 mm or more.
- the obtained steel sheet was excellent in both magnetic flux density and magnetostriction, even though a temperature gradient was applied to the steel sheet during secondary recrystallization.
- the obtained grain-oriented electrical steel sheet had an extremely small deviation between the crystal orientation of the secondary recrystallized grains and the ideal Goss orientation, and that the angle deviation ⁇ was small on average at each measurement point along the rolling direction L, the crystal grains did not grow coarsely in the rolling direction L, and the shape of the crystal grains had a tendency to elongate in the direction perpendicular to the rolling C and to be flattened in the rolling direction L.
- the coarse Goss-oriented grains (Goss-oriented grains with large crystal grain size) close to the ideal Goss orientation grow preferentially. Therefore, even if the secondary recrystallized grains are not grown large, a steel sheet occupied by secondary recrystallized grains close to the ideal Goss orientation can be obtained.
- the size, shape, and arrangement of the crystal grains after secondary annealing can be controlled by appropriately arranging the local heat affected zones on the steel sheet surface.
- a steel sheet with a small grain size (particularly the grain size D L in the rolling direction) of the Goss-oriented grains at the end of secondary annealing can be obtained.
- the Goss orientation grains that grow preferentially from the local heat affected region have a crystal orientation close to the ideal Goss orientation, so that good magnetic flux density can be obtained even though the secondary recrystallized grain size is small.
- the crystal grains are prevented from growing coarsely in the rolling direction L, so that the deterioration of the misalignment angle ⁇ due to coil setting can be suppressed, and good magnetostriction characteristics can be obtained.
- the grain-oriented electrical steel sheet described above can increase the degree of accumulation in the Goss orientation while suppressing the coarsening of the secondary recrystallized grain size (particularly the grain size D L in the rolling direction), so that it is not necessary to perform or can reduce the magnetic domain width refinement by strain introduction or groove formation.
- the magnetic domain refinement effect can be preferably obtained by the grain boundaries that increase with the refinement of the secondary recrystallized grain size, the magnetic domains are refined without applying the conventional magnetic domain control technology. Therefore, unlike the conventional magnetic domain control technology, it is not necessary to introduce strain into the steel sheet or it can be reduced, so that it is possible to prevent an increase in magnetostriction.
- the grain-oriented electrical steel sheet described above can be used for applications requiring strain relief annealing at 800°C or more.
- the grain-oriented electrical steel sheet according to this embodiment has excellent iron loss characteristics because it is possible to obtain a favorable magnetic domain refinement effect due to the grain boundaries that increase with the refinement of the secondary recrystallized grain size (particularly the grain size D L in the rolling direction).
- the method for manufacturing the grain-oriented electrical steel sheet according to this embodiment is not limited to the method described below.
- the manufacturing method described below is one example for manufacturing the grain-oriented electrical steel sheet according to this embodiment.
- the steps and quantitative conditions for each step shown below are examples adopted to demonstrate the feasibility of this embodiment, and this embodiment is not limited to these steps and quantitative values.
- the manufacturing method for grain-oriented electrical steel sheet according to this embodiment may adopt various conditions as long as they do not deviate from the gist of this embodiment and achieve the purpose of this embodiment.
- the manufacturing method of the grain-oriented electrical steel sheet according to this embodiment can apply the conventional known manufacturing method of grain-oriented electrical steel sheet as a basic process.
- examples of conventional manufacturing methods of grain-oriented electrical steel sheet include a manufacturing method in which inhibitors such as MnS and AlN are formed by high-temperature slab heating, and a manufacturing method in which AlN inhibitors are formed by low-temperature slab heating and nitriding treatment.
- the manufacturing method of the grain-oriented electrical steel sheet according to this embodiment is not limited to a specific manufacturing method. Below, a method of applying nitriding treatment as a low-temperature slab heating process will be described.
- a slab is prepared.
- An example of a method for producing a slab is as follows. Molten steel is produced (smelted). A slab is produced using the molten steel. The slab may be produced by a continuous casting method. An ingot may be produced using the molten steel, and the ingot may be bloomed to produce a slab.
- the thickness of the slab is not particularly limited. The thickness of the slab is, for example, 150 to 350 mm. The thickness of the slab is preferably 220 to 280 mm. As the slab, a so-called thin slab having a thickness of 10 to 70 mm may be used. When a thin slab is used, rough rolling before finish rolling can be omitted in the hot rolling process.
- the above slab may contain the following elements in its chemical composition:
- Carbon (C) is an effective element for controlling the primary recrystallized structure in the manufacturing process, but if its content in the final product is excessive, it will have a detrimental effect on the magnetic properties.
- the preferred upper limit of the C content is 0.075%.
- C is purified in the decarburization annealing process and the finish annealing process to be 0.005% or less.
- the lower limit of the C content may be more than 0%, or may be 0.001%.
- Si 2.0-7.0%
- Silicon (Si) increases the electrical resistance of grain-oriented electrical steel sheets and reduces iron loss. If the Si content is less than 2.0%, ⁇ transformation occurs during final annealing, and the crystallization of the grain-oriented electrical steel sheets is reduced. On the other hand, if the Si content exceeds 7.0%, the cold workability decreases and cracks tend to occur during cold rolling.
- the upper limit of the Si content is preferably 4.5%, and more preferably 4.0%.
- Mn 0.05-1.00%
- Manganese (Mn) combines with S or Se to produce MnS or MnSe, and functions as an inhibitor.
- Mn is contained, the Mn content is within the range of 0.05 to 1.00%.
- the secondary recrystallization is stable. It is possible for part of the inhibitor function to be performed by a nitride of an Nb group element. In this case, the strength of MnS or MnSe as a general inhibitor is Therefore, the upper limit of the Mn content is preferably 0.50%, and more preferably 0.20%.
- At least one of S and Se 0.003 to 0.035% in total Sulfur (S) and selenium (Se) combine with Mn to produce MnS or MnSe, which functions as an inhibitor.
- S and Se When at least one of S and Se is contained, if the total content of S and Se is 0.003 to 0.035%, secondary recrystallization is stable. It is possible for a part of the inhibitor function to be borne by a nitride of an Nb group element. In this case, the strength of MnS or MnSe as a general inhibitor is controlled to be weak. For this reason, the preferred upper limit of the total content of S and Se is 0.025%, and more preferably 0.010%. If S and Se remain after the final annealing, they form compounds and deteriorate the iron loss. Therefore, it is preferable to reduce S and Se as much as possible by purification during the final annealing.
- the total content of S and Se means that at least one of S and Se is included, and is the total content.
- Al 0.010-0.065%
- Aluminum (Al) combines with N to precipitate as (Al,Si)N, and functions as an inhibitor.
- the Al content is within the range of 0.010 to 0.065%.
- AlN formed as an inhibitor by nitriding, which will be described later expands the secondary recrystallization temperature range, and secondary recrystallization is particularly stable in the high temperature range. Therefore, the Al content is 0.010 to 0.065
- the lower limit of the Al content is preferably 0.020%, and more preferably 0.025%.
- the upper limit of the Al content is preferably 0.040%. and more preferably 0.035%.
- N 0.012% or less Nitrogen (N) combines with Al to function as an inhibitor. Since N can be contained by nitriding during the manufacturing process, no lower limit is specified. For example, the lower limit of the N content may be more than 0%, or may be 0.001%. On the other hand, when N is contained, if the N content exceeds 0.012%, blisters, which are a type of defect, tend to occur in the steel sheet. The preferred upper limit of the N content is 0.010%, and more preferably 0.009%. N is purified in the final annealing process, and becomes 0.005% or less after the final annealing process.
- the balance of the above chemical composition consists of Fe and impurities.
- impurities refers to elements that are mixed in from raw materials such as ore and scrap during industrial production of steel, or from the production environment, etc.
- the upper limit of the total impurity content may be, for example, 5%.
- the above-mentioned chemical composition may contain known optional elements in place of part of Fe, taking into consideration not only solving manufacturing problems, but also strengthening the inhibitor function through compound formation and the effect on magnetic properties.
- optional elements that may be contained in place of part of Fe include the following elements:
- Nb group elements 0.050% or less
- the total content of Nb group elements (one or more of Nb, V, Mo, Ta, and W) may be 0.050% or less.
- the total content of Nb group elements is 0.030% or less, since secondary recrystallization is started at an appropriate timing.
- the orientation of the secondary recrystallized grains generated becomes very favorable, and the structure can be finally controlled to be favorable for magnetic properties.
- Nb and Ta have a strong effect and are preferable.
- the total content of Nb group elements is more preferably 0.004 to 0.020%. Even more preferably, it is 0.005 to 0.010%.
- the total content of Nb group elements means the total content including at least one of Nb, V, Mo, Ta, and W.
- the slab also contains, as optional elements, in mass %: Cu: 0.40% or less, Bi: 0.010% or less, B: 0.080% or less, P: 0.50% or less, Ti: 0.015% or less, Sn: 0.10% or less, Sb: 0.10% or less, Cr: 0.30% or less, Ni: 1.00% or less. Since these optional elements may be contained according to known purposes, there is no need to set a lower limit for the content of the optional elements, and the lower limit may be 0%.
- the chemical composition of the above slabs can be measured by the above analytical method, just like the chemical composition of the final product, grain-oriented electrical steel sheet.
- the hot rolling process is a process in which a slab heated to a predetermined temperature (e.g., 1100 to 1400°C) is hot-rolled to obtain a hot-rolled steel sheet.
- a predetermined temperature e.g. 1100 to 1400°C
- the silicon steel material (slab) heated in the heating process is roughly rolled, and then finish-rolled to obtain a hot-rolled steel sheet with a predetermined thickness, for example, 1.8 to 3.5 mm. After the finish rolling is completed, the hot-rolled steel sheet is coiled at a predetermined temperature.
- the slab heating temperature should be set to 1100°C to 1280°C.
- the hot-rolled sheet annealing process is a process in which the hot-rolled steel sheet obtained in the hot rolling process is annealed under a predetermined temperature condition (for example, at 750 to 1200 ° C for 30 seconds to 10 minutes) to obtain an annealed steel sheet.
- Hot-rolled sheet annealing is generally performed to control the steel sheet structure such as the recrystallization rate, residual strain, and crystal grain size by annealing the hot-rolled steel sheet after the hot rolling process, and to preferably adjust the precipitate form in the steel.
- a high-temperature slab heating process it is a process for finally controlling the form of precipitates such as AlN, and conditions are adjusted so that they precipitate uniformly and finely.
- the hot-rolled sheet annealing for example, after heating the steel sheet to 1050 ° C to 1150 ° C, in order to properly precipitate AlN, etc., it may be cooled slowly to an intermediate temperature (850 ° C to 950 ° C) for 50 to 150 seconds, and then cooled with water.
- an intermediate temperature 850 ° C to 950 ° C
- the cold rolling process is a process in which the annealed steel sheet obtained in the hot-rolled sheet annealing process is subjected to one cold rolling or multiple cold rolling (two or more times) via annealing (intermediate annealing) to obtain a cold-rolled steel sheet having a thickness of, for example, 0.10 to 0.50 mm.
- the interpass temperature of the cold rolling may be set to about 100° C. to 300° C.
- local rapid heating is performed on the cold-rolled steel sheet after the cold rolling process to form a local heating region.
- the rapid heating method is not particularly limited as long as it can locally heat the steel sheet.
- a method of heating by contacting a spot electrode with the front and back surfaces of the steel sheet and passing an electric current through the steel sheet a method of heating by irradiating the surface of the steel sheet with laser light or an electron beam, a method of locally heating by induction heating, a method of heating by contacting a hot piece, etc. can be adopted.
- each local heating region can be a dot-like region with a diameter of about 10 ⁇ m to 10 mm, or a linear region with a width of about 10 ⁇ m to 10 mm.
- the electrode used for current heating may be a circular electrode as described above, or a linear electrode.
- the minimum diameter and width of the size of the locally heated region depend on the shape of the spot electrode and the technology for reducing the focused diameter of the laser light or electron beam. In principle, it is possible to further reduce the size of the locally heated region, but considering that the current size of the nuclei of recrystallized grains is about 1 ⁇ m, it is believed that an effect can be obtained if the size of the locally heated region is 1 ⁇ m or more. From an industrial perspective, the above minimum diameter and width should be 10 ⁇ m or more. Regarding the size of the locally heated region, if the maximum diameter or width exceeds 10 mm, the area proportion of Goss orientation grains with relatively large angle deviations ⁇ and ⁇ that cannot grow outside the locally heated region increases. In this case, it becomes difficult to obtain the effect of local rapid heating.
- the heating rate should be 500°C/sec or more in the center of the locally heated region as viewed in the thickness direction and at 1/5 of the thickness of the steel plate. If the heating rate in the above region is 500°C/sec or more, the structure of the locally heated region can be preferably controlled to a recovered structure or a recrystallized structure.
- the above heating rate is preferably 2000°C/sec or more, and more preferably 10000°C/sec or more.
- the upper limit of the above heating rate is not particularly limited, and may be, for example, 1,000,000°C/sec.
- the aim is to have coarse Goss oriented grains in the local heat affected region after decarburization annealing, but if the heating rate during decarburization annealing is faster than the heating rate during local rapid heating, it is difficult to achieve the above objective. Therefore, although it depends on the magnitude of the heating rate, it is preferable to set the heating rate during local rapid heating to be equal to or higher than the heating rate during decarburization annealing.
- the 1/5 part of the thickness of the steel plate mentioned above refers to a depth equivalent to 1/5 of the thickness of the steel plate from the surface of the steel plate in the thickness direction.
- the maximum temperature reached should be 700°C or higher in the center of the locally heated region when viewed from the plate thickness direction and at 1/5 of the plate thickness of the steel plate. If the maximum temperature reached in the above region is 700°C or higher, the structure of the locally heated region can be preferably controlled to a recovered structure or a recrystallized structure.
- the above maximum temperature reached is preferably 800°C or higher, and more preferably 900°C or higher.
- the above maximum temperature reached should be below the melting point of the steel plate, for example, 1400°C or lower.
- the holding time from reaching the maximum temperature to cooling to 700°C at the center of the locally heated region as viewed from the thickness direction and at 1/5 of the thickness of the steel plate should be 0.1 seconds or more. If the holding time in the above region is 0.1 seconds or more, the structure of the locally heated region can be preferably controlled to a recovered structure or a recrystallized structure.
- the holding time is preferably 0.2 seconds or more, more preferably 0.3 seconds or more, and even more preferably 0.4 seconds or more.
- there is no particular limit to the upper limit of the holding time and it may be, for example, 10 seconds or less.
- the holding time from reaching the maximum temperature to cooling to 700°C has a fundamental effect on the formation of coarse Goss orientation grains close to the ideal Goss orientation.
- the method of local rapid heating is not particularly limited.
- local rapid heating may be performed by spot electrical current heating, laser irradiation, or electron beam irradiation.
- it is sufficient to control the heating rate, maximum temperature, and holding time described above so as to satisfy the above.
- a person skilled in the art can combine the various conditions of the local rapid heating method to control the desired heating rate, maximum temperature, and holding time.
- a person skilled in the art can perform a heat conduction analysis using the finite element method to control the heating rate and maximum temperature reached in the center of the localized heating area when viewed from the plate thickness direction and at 1/5 of the plate thickness of the steel plate.
- a person skilled in the art can control the above-mentioned holding time by adjusting the heat removal conditions after the maximum temperature is reached. For example, in the case of spot current heating, the electrode holding time after current is controlled, or the shape of the spot electrode can be changed to a shape suitable for heat removal.
- the irradiation speed can be adjusted, or the shape of the irradiation area can be changed to an ellipse or the like to gradient the irradiation energy from the center to the outer edge of the irradiation area.
- the heating by laser irradiation preferentially heats only the vicinity of the irradiated steel sheet surface, and the inside of the steel sheet is not easily heated.
- the heating by laser irradiation is non-contact heating, the heat is removed quickly after heating, and the temperature is not easily maintained. Therefore, when performing laser irradiation heating as local rapid heating, in order to recover or recrystallize the cold-worked structure in the laser irradiated region, it is necessary to control the conditions so that not only the surface of the steel sheet but also the inside of the steel sheet is heated, and the cooling rate is slowed down to relatively coarsen the subgrain structure in the laser irradiated region.
- the laser irradiation conditions for performing local rapid heating are completely different from the laser irradiation conditions for performing magnetic domain refinement. For example, even if the laser irradiation conditions for performing magnetic domain refinement (usually 0.5 to 50 mJ/mm 2 ) are applied to this embodiment, the structure of the locally heated region is not favorably controlled, and coarse Goss orientation grains close to the ideal Goss orientation are not formed in the steel sheet after the decarburization annealing process. The same applies to electron beam irradiation as to laser irradiation.
- the structure of the locally heated region is not favorably controlled, and coarse Goss oriented grains close to the ideal Goss orientation are not formed in the steel sheet after the decarburization annealing process.
- the local heat affected zones on the steel sheet surface may be appropriately arranged according to the purpose.
- the shape of the secondary recrystallized grains may be controlled so that they extend in the direction perpendicular to the rolling direction C and have a tendency to be flattened in the rolling direction L.
- the larger the interval between the local heat affected zones in the rolling direction L the more likely the secondary recrystallized grain size will be coarse in the rolling direction L.
- the larger the interval between the local heat affected zones in the direction perpendicular to the rolling direction C the more likely the secondary recrystallized grain size will be coarse in the direction perpendicular to the rolling direction C.
- the arrangement of these local heat affected zones in the rolling direction L and the direction perpendicular to the rolling direction C affect each other.
- the secondary recrystallized grain size may be coarse in the direction perpendicular to the rolling direction C.
- the chemical composition of the steel and the temperature gradient in the heating process of the finish annealing described later also affect the grain growth of the secondary recrystallized grains. Therefore, these conditions may be controlled in a composite manner to control the above-mentioned flat shape.
- a person skilled in the art can control the flat shape of secondary recrystallized grains by appropriately adjusting the arrangement of the local heat affected zone and other conditions.
- decarburization annealing process In the decarburization annealing step, the cold-rolled steel sheet after the local rapid heating step is subjected to decarburization annealing (primary annealing). This decarburization annealing increases the frequency of Goss-oriented grains formed in the local heat-affected zone, increases the grain size of the Goss-oriented grains, and preferably forms coarse Goss-oriented grains having an orientation close to the ideal Goss orientation.
- the decarburization annealing conditions may be a heating rate of 10 to 10,000°C/sec, an annealing temperature of 700 to 900°C, and an annealing time of 10 to 600 seconds.
- C contained in the cold-rolled steel sheet is removed. It is preferable to perform the decarburization annealing in a moist atmosphere in order to remove "C" contained in the cold-rolled steel sheet.
- the primary recrystallized grain size is not particularly limited, but is preferably 8 to 30 ⁇ m.
- the heating rate of decarburization annealing may be 10,000°C/sec or less, but it is preferable to slow down the heating rate of decarburization annealing to form ⁇ 111 ⁇ 112> orientation grains and ⁇ 411 ⁇ 148> orientation grains that are easily eroded into the matrix portion (region not affected by local heat).
- the heating rate of decarburization annealing is preferably 300°C/sec or less, more preferably 200°C/sec or less, and even more preferably 100°C/sec or less.
- the degree of oxidation (PH 2 O/PH 2 ) in the annealing atmosphere may be set to 0.01 to 0.15.
- the degree of oxidation PH 2 O/PH 2 can be defined as the ratio of the water vapor partial pressure PH 2 O to the hydrogen partial pressure PH 2 in the atmosphere.
- Nitriding is an effective treatment in a low-temperature slab heating process in which the slab heating temperature is 1280°C or less, and is an important step for adjusting the strength of the inhibitor in secondary recrystallization. Nitriding increases the nitrogen content of the steel sheet by about 40 to 200 ppm between the start of the decarburization treatment and the start of secondary recrystallization in the finish annealing.
- Examples of nitriding include a treatment of annealing in an atmosphere containing a gas with nitriding ability such as ammonia, and a treatment of finish annealing a decarburized annealed steel sheet coated with an annealing separator containing a powder with nitriding ability such as MnN.
- the amount of nitriding after the nitriding treatment is preferably 130 to 350 ppm, and more preferably 150 to 250 ppm.
- the annealing separator application process is a process of applying an annealing separator to the decarburized annealed steel sheet.
- an annealing separator mainly composed of MgO or an annealing separator mainly composed of Al 2 O 3 can be used.
- the decarburized annealed steel sheet after application of the annealing separator is wound into a coil and is finish annealed in the next finish annealing process.
- the final annealing process is a process in which the decarburized annealed steel sheet coated with the annealing separator is subjected to final annealing (secondary annealing) to cause secondary recrystallization.
- second annealing final annealing
- the growth of the primary recrystallized grains is suppressed by an inhibitor, and the secondary recrystallization is allowed to proceed, thereby preferentially growing ⁇ 100 ⁇ 001> oriented grains and dramatically improving the magnetic flux density.
- the decarburized annealed steel sheet that has been coated with an annealing separator and dried may be held at a temperature range of 1000°C to 1300°C for 10 hours to 60 hours.
- the atmosphere during the final annealing may be, for example, a nitrogen atmosphere or a mixed atmosphere of nitrogen and hydrogen.
- secondary recrystallization may be caused by applying a temperature gradient of more than 0.5°C/cm, preferably 1.0°C/cm or more, to the boundary between the primary recrystallized region and the secondary recrystallized region in the steel sheet during the heating process of the finish annealing.
- a temperature gradient may be applied to the steel sheet during the growth of secondary recrystallized grains in a temperature range of 800°C or higher during the heating process of the finish annealing.
- the direction in which the above temperature gradient is applied may be the direction C perpendicular to the rolling.
- the above temperature gradient may be changed appropriately depending on the chemical composition of the steel.
- the temperature gradient may be more than 0.5°C/cm (preferably 1.0°C/cm or more), while if the chemical composition is such that secondary recrystallized grains tend not to grow preferentially, the temperature gradient is preferably more than 1.0°C/cm.
- the method of providing a temperature gradient is not particularly limited, and any known method may be applied.
- the position and arrangement of the heating device and the temperature distribution in the annealing furnace may be controlled so that a sufficient temperature difference is generated from the top to the bottom of the coil, or from the outside to the inside.
- a temperature distribution may be formed in the coil being annealed by actively heating only a portion of the coil using induction heating, high-frequency heating, or electrical heating devices.
- secondary recrystallized grains with sharp orientations will be generated from the parts of the coil that have reached the secondary recrystallization start state early, and these secondary recrystallized grains will grow preferentially due to the temperature gradient.
- the secondary recrystallized grains can be made to grow throughout the entire coil.
- a coating solution containing phosphoric acid or a phosphate, chromic anhydride or a chromate, and colloidal silica is applied to the steel sheet after the final annealing and baked (for example, at 350° C. to 1150° C. for 5 to 300 seconds), An insulating coating is formed.
- the grain-oriented electrical steel sheet according to this embodiment can be manufactured by the above steps.
- the grain-oriented electrical steel sheet according to this embodiment which is manufactured by controlling the conditions of each step in a complex and inseparable manner, has an extremely small deviation between the crystal orientation of the secondary recrystallized grains and the ideal Goss orientation, an average small angle deviation ⁇ at each measurement point along the rolling direction L, the crystal grains do not grow coarse with respect to the rolling direction L, and the shape of the crystal grains tends to be elongated in the direction perpendicular to the rolling C and flattened in the rolling direction L. Therefore, despite the temperature gradient being applied to the steel sheet during secondary recrystallization, it has excellent magnetic flux density and magnetostriction.
- the conditions in the examples are one example of conditions adopted to confirm the feasibility and effects of the present invention, and the present invention is not limited to this one example of conditions.
- Various conditions can be adopted in the present invention as long as they do not deviate from the gist of the present invention and the object of the present invention is achieved.
- the chemical composition-adjusted slabs were used as the raw material to manufacture decarburized annealed steel sheets with the chemical compositions shown in Table 2. These chemical compositions were measured based on the method described above. In Table 2, "-" indicates that no control or manufacturing was carried out with the content in mind, and that no content measurements were carried out.
- the slabs were heated to 1150°C and subjected to hot rolling to obtain hot-rolled steel sheets with a thickness of 2.6 mm.
- the hot-rolled steel sheets were then heated to 1100°C and subsequently annealed at 900°C for hot-rolled sheet annealing, after which the sheets were pickled to remove the scale formed on the surface.
- These steel sheets were subjected to one cold rolling or multiple cold rolling with intermediate annealing in between to obtain cold-rolled steel sheets with a final thickness of 0.22 mm.
- the above cold-rolled steel sheets were subjected to localized rapid heating under the conditions shown in Tables 3 to 7.
- spot current heating a copper electrode with a diameter of 1 mm was used in the contact area with the steel sheet, and the electrode shape, electrode pressure, current, current duration, and electrode holding time after current were varied in a composite manner to control the heating rate, maximum temperature, and holding time from reaching the maximum temperature until cooling to 700°C (holding time above 700°C).
- the laser heating a fiber laser was used, and the focal spot diameter of the laser light in the rolling direction (i.e., the diameter including 86% of the laser output) was set to 30 ⁇ m (except for Tests No. 71 and No. 72).
- the laser irradiation energy density, laser scanning speed, and shape of the laser irradiation area were varied in a composite manner to control the heating rate, maximum temperature, and holding time above 700°C.
- Those skilled in the art can combine the conditions of the localized rapid heating method to control the desired heating rate, maximum temperature, and holding time above 700°C.
- test No. 70 general laser irradiation conditions for magnetic domain refinement were applied.
- test No. 71 the focusing spot diameter was set to 0.5 mm, the laser irradiation energy density was set to 2.0 J/mm 2 , and the laser beam irradiation portion was controlled so that it would eventually become the grain boundary of the secondary recrystallized grain.
- the focusing spot diameter was set to 0.5 mm
- the laser irradiation energy density was set to 30.0 J/mm 2
- the laser beam irradiation portion was controlled so that it would finally become the grain boundary of the secondary recrystallized grain.
- the local heating condition “Linear or spotted” indicates the shape of the localized heated area on the surface of the cold-rolled steel sheet
- the local heating conditions “Rolling direction spacing” and “Width direction spacing” indicate the spacing in the rolling direction and transverse direction at which the localized heated areas are arranged on the surface of the cold-rolled steel sheet.
- the localized heated areas are arranged at equal intervals in the rolling direction and transverse direction. Note that when providing localized heated areas on the surface of the cold-rolled steel sheet, they are arranged so that the distribution of the localized heated areas is not uneven.
- the widthwise spacing of the localized heating conditions for localized rapid heating, "end 10,” indicates that a localized heating area was formed only at a position 10 mm from the end of the steel plate in the direction perpendicular to the rolling direction.
- the cold-rolled steel sheets after the localized rapid heating were subjected to decarburization annealing under the conditions shown in Tables 3 to 7.
- the degree of oxidation (PH 2 O/PH 2 ) in the annealing atmosphere (furnace atmosphere) was set to 0.13.
- the decarburized annealed steel sheets produced were nitrided at 750°C in a nitrogen-hydrogen-ammonia atmosphere to set the nitrogen content of the steel sheets to 220 ppm.
- An annealing separator mainly composed of MgO was then applied, and finish annealing was performed.
- the steel sheet was heated to 1000°C at 15°C/hr (°C/hour) in a mixed atmosphere of hydrogen and nitrogen, and then heated to 1200°C at the heating rate shown in Tables 3 to 7.
- a temperature gradient shown in Tables 3 to 7 was applied in the direction perpendicular to the rolling C to the boundary between the primary recrystallization region and the secondary recrystallization region in the steel sheet.
- a temperature gradient of " ⁇ 1.0" for the heating process for finish annealing indicates that the temperature gradient in the heating process was not substantially controlled.
- the steel sheet was held at 1200°C for 20 hr (hours) in a hydrogen atmosphere.
- the steel sheet After final annealing, the steel sheet is coated with an insulating coating solution made mainly of colloidal silica and phosphate, with chromic anhydride added as needed, and baked to form an insulating coating.
- an insulating coating solution made mainly of colloidal silica and phosphate, with chromic anhydride added as needed, and baked to form an insulating coating.
- the chemical composition of the base steel sheet, the average value ave ⁇ L of the angle deviation ⁇ , the number-based 10% grain size DL 10 of the grain size DL , and the average value aveD C of the grain size DC were measured based on the methods described above.
- the results are shown in Tables 7 to 13.
- "-" indicates that no control or production was performed with the content in mind, and that no content measurement was performed.
- various characteristics were evaluated for the produced grain-oriented electrical steel sheets. The evaluation results are shown in Tables 7 to 12.
- the magnetic properties of the grain-oriented electrical steel sheets were measured based on the single sheet magnetic properties test method (SST: Single Sheet Tester) specified in JIS C 2556:2015.
- magnetostriction ⁇ p-p@1.7T difference between minimum and maximum magnetostriction at 1.7T generated in the steel sheet was measured under conditions of AC frequency: 50 Hz and excitation magnetic flux density: 1.7 T.
- ⁇ p-p@1.7T (L max -L min ) ⁇ L 0 .
- the magnetostriction rate level at 1.7 T was determined based on the magnetic characteristic values described above.
- the magnetostriction rate level Lva (unit: dB) was calculated using the magnetostriction amount ⁇ (fi) (0 Hz to 3.2 kHz) obtained for each frequency by Fourier transforming the magnetostriction waveform with two or more periods and acquired at a sampling frequency of 6.4 kHz, using the following formula 1.
- the magnetostriction rate level Lva was examined for the 200 Hz component.
- ⁇ density of air (kg/m 3 )
- c speed of sound (m/sec)
- P 0 The minimum pressure (Pa) at which a human can hear a 1 kHz sound.
- fi frequency (Hz)
- ⁇ (fi) Magnetostriction amount for each frequency obtained by Fourier transform
- ⁇ (fi) A characteristic of frequency fi ⁇ : Circular constant
- the grain-oriented electrical steel sheets according to the present invention had favorably controlled ave ⁇ L , DL 10 , and aveD C. All of these examples according to the present invention were excellent in magnetic flux density and magnetostriction characteristics. They were also excellent in iron loss.
- the grain-oriented electrical steel sheets as comparative examples did not have favorable control of ave ⁇ L , D L 10 , or aveD C. These comparative examples did not provide favorable magnetic flux density or magnetostriction characteristics as grain-oriented electrical steel sheets.
- the above-mentioned aspect of the present invention makes it possible to provide a grain-oriented electrical steel sheet that is excellent in both magnetic flux density and magnetostriction properties, even when a technology that applies a temperature gradient to the steel sheet during secondary recrystallization is applied, and therefore has high industrial applicability.
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Abstract
Description
本願は、2023年6月29日に、日本に出願された特願2023-106860号に基づき優先権を主張し、その内容をここに援用する。
圧延面法線方向Zを回転軸とする理想ゴス方位からのずれ角をαと定義し、
圧延直角方向Cを回転軸とする理想ゴス方位からのずれ角をβと定義し、
圧延方向Lを回転軸とする理想ゴス方位からのずれ角をγと定義し、
板面上の1つの測定点で測定する結晶方位のずれ角を(α β γ)と表し、
前記1つの測定点における角度偏差をφ=(α2+β2)1/2と定義し、
圧延方向Lに沿って間隔が1mmの複数の測定点で求めた角度偏差φの平均値をaveφLと定義したとき、
前記aveφLが、aveφL≦3.5°を満たし、
前記板面上で隣接し且つ間隔が1mmである2つの測定点で測定する結晶方位のずれ角を(α1 β1 γ1)および(α2 β2 γ2)と表し、
[(α2-α1)2+(β2-β1)2+(γ2-γ1)2]1/2≧1.0°を満足する2つの測定点の中間点を粒界GBと定義し、
前記粒界GBに基づいて求める圧延方向Lの粒径を単位mmでDLと定義し、
圧延方向Lに沿って求めた粒径DLを大きい順に並べて大きい方から個数基準で10%となる粒径を単位mmでDL10と定義したとき、
前記DL10が、DL10≦100-15×aveφLを満たし、
前記粒界GBに基づいて求める圧延直角方向Cの粒径を単位mmでDCと定義し、
圧延直角方向Cに沿って求めた粒径DCの平均値をaveDCと定義したとき、
前記aveDCが、aveDC≧50を満たす。
圧延面法線方向Zを回転軸とする理想ゴス方位からのずれ角をαと定義し、
圧延直角方向Cを回転軸とする理想ゴス方位からのずれ角をβと定義し、
圧延方向Lを回転軸とする理想ゴス方位からのずれ角をγと定義し、
板面上の1つの測定点で測定する結晶方位のずれ角を(α β γ)と表し、
上記1つの測定点における角度偏差をφ=(α2+β2)1/2と定義し、
圧延方向Lに沿って間隔が1mmの複数の測定点で求めた角度偏差φの平均値をaveφLと定義したとき、
上記aveφLが、aveφL≦3.5°を満たす。
上記板面上で隣接し且つ間隔が1mmである2つの測定点で測定する結晶方位のずれ角を(α1 β1 γ1)および(α2 β2 γ2)と表し、
[(α2-α1)2+(β2-β1)2+(γ2-γ1)2]1/2≧1.0°を満足する2つの測定点の中間点を粒界GBと定義し、
上記粒界GBに基づいて求める上記圧延方向Lの粒径を単位mmでDLと定義し、
上記圧延方向Lに沿って求めた粒径DLを大きい順に並べて大きい方から個数基準で10%となる粒径を単位mmでDL10と定義したとき、
上記DL10が、DL10≦100-15×aveφLを満たす。
上記粒界GBに基づいて求める上記圧延直角方向Cの粒径を単位mmでDCと定義し、
上記圧延直角方向Cに沿って求めた粒径DCの平均値をaveDCと定義したとき、
上記aveDCが、aveDC≧50を満たす。
Si:2.0~7.0%、
C:0~0.0050%、
Mn:0~1.0%、
S及びSe:合計で0~0.0150%、
Al:0~0.0650%、
N:0~0.0050%、
Nb、V、Mo、Ta、及びW:合計で0~0.050%、
Cu:0~0.40%、
Bi:0~0.010%、
B:0~0.080%、
P:0~0.50%、
Ti:0~0.0150%、
Sn:0~0.10%、
Sb:0~0.10%、
Cr:0~0.30%、
Ni:0~1.0%、
を含有し、残部がFeおよび不純物からなればよい。
Si(シリコン)は、母材鋼板にとって基本元素である。Si含有量が2.0%未満であると、渦電流損を十分に低減できないため、良好な磁気特性が得られない。そのため、母材鋼板のSi含有量は2.0%以上とする。Si含有量は、好ましくは2.50%以上、より好ましくは3.0%以上である。一方で、Si含有量が7.0%を超えると、鋼板が脆化し、製造に際して通板性が顕著に劣化するので、母材鋼板のSi含有量は7.0%以下とする。Si含有量は、好ましくは4.50%以下、より好ましくは4.0%以下である。
C(炭素)は、母材鋼板にとって選択元素である。Cは鋼片(スラブ)に含有されるが、仕上げ焼鈍後の母材鋼板にCが過剰に残留すると、良好な鉄損特性が得られないことがある。そのため、母材鋼板のC含有量は0.0050%以下であればよい。C含有量は、好ましくは0.0040%以下、より好ましくは0.0030%以下である。一方で、母材鋼板のC含有量の下限値は、特に制限されず、0%であればよい。ただ、C含有量を0%にすることは工業的に容易ではないので、C含有量を、0%超としてもよく、0.00010%以上としてもよい。
Mn(マンガン)は、母材鋼板にとって選択元素である。Mnは鋼片(スラブ)に含有されるが、過剰に含有されると、二次再結晶焼鈍時に鋼が相変態し、二次再結晶が十分に進行せず、良好な磁気特性が得られないことがある。そのため、母材鋼板のMn含有量は1.0%以下であればよい。Mn含有量は、好ましくは0.50%以下、より好ましくは0.20%以下である。一方で、母材鋼板のMn含有量の下限値は、特に制限されず、0%であればよい。ただ、Mnは、MnSやMnSeを形成して二次再結晶時のインヒビターとしての効果を有するので、Mn含有量を、0%超としてもよく、0.00010%以上としてもよい。
S(硫黄)及びSe(セレン)は、母材鋼板にとって選択元素である。S及びSeは鋼片(スラブ)に含有されるが、仕上げ焼鈍後の母材鋼板にS及びSeが過剰に残留すると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のS及びSeの合計含有量は0.0150%以下であればよい。S及びSeの合計含有量は、好ましくは0.010%以下、より好ましくは0.0050%以下である。一方で、母材鋼板のS及びSeの合計含有量の下限値は、特に制限されず、0%であればよい。ただ、S及びSeは、MnSやMnSeを形成して二次再結晶時のインヒビターとしての効果を有するので、S及びSeの合計含有量を、0%超としてもよく、0.00010%以上としてもよい。
Al(アルミニウム)は、母材鋼板にとって選択元素である。Alは鋼片(スラブ)に含有されるが、仕上げ焼鈍後の母材鋼板にAlが過剰に残留すると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のAl含有量は0.0650%以下であればよい。Al含有量は、好ましくは0.040%以下、より好ましくは0.035%以下である。一方で、母材鋼板のAl含有量の下限値は、特に制限されず、0%であればよい。ただ、Alは、AlNを形成して二次再結晶時のインヒビターとしての効果を有するので、Al含有量を、0%超としてもよく、0.00010%以上としてもよい。なお、上記のAl含有量は、酸可溶性Al(sol.Al)である。
N(窒素)は、母材鋼板にとって選択元素である。Nは鋼片(スラブ)に含有されるが、仕上げ焼鈍後の母材鋼板にNが過剰に残留すると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のN含有量は0.0050%以下であればよい。N含有量は、好ましくは0.0040%以下、より好ましくは0.0030%以下である。一方で、母材鋼板のN含有量の下限値は、特に制限されず、0%であればよい。ただ、Nは、AlNを形成して二次再結晶時のインヒビターとしての効果を有するので、N含有量を、0%超としてもよく、0.00010%以上としてもよい。
Nb(ニオブ)、V(バナジウム)、Mo(モリブデン)、Ta(タンタル)、W(タングステン)は、母材鋼板にとって選択元素である。母材鋼板にNb群元素(Nb、V、Mo、Ta、及びWの1種以上)が過剰に残留すると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のNb、V、Mo、Ta、及びWの合計含有量は、0.050%以下であればよい。Nb群元素は、好ましくは0.030%以下、好ましくは0.020%以下、より好ましくは0.010%以下である。一方で、母材鋼板のNb、V、Mo、Ta、及びWの合計含有量は、特に制限されず、0%であればよい。ただ、Nb、V、Mo、Ta、またはWは、炭化物や窒化物や炭窒化物を形成して二次再結晶時のインヒビターとしての効果を有するので、Nb、V、Mo、Ta、及びWの合計含有量を、0%超としてもよく、0.003%以上としてもよい。
Cu(銅)は、母材鋼板にとって選択元素である。Cu含有量が0.40%を超えると、熱間圧延中、鋼板が脆化することがある。そのため、母材鋼板のCu含有量は0.40%以下であればよい。Cu含有量は、好ましくは0.30%以下、より好ましくは0.10%以下である。一方で、Cu含有量の下限値は、特に制限されず、0%であればよい。ただ、Cuは、Goss方位の集積度を高めて、磁気特性を改善させる効果を有するので、Cu含有量は、0%超としてもよく、0.010%以上としてもよい。
Bi(ビスマス)は、母材鋼板にとって選択元素である。Bi含有量が0.010%を超えると、被膜密着性が低下することがある。また、仕上げ焼鈍時の純化が不十分でBiが過剰に残留すると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のBi含有量は0.010%以下であればよい。Bi含有量は、好ましくは0.0050%以下、より好ましくは0.0020%以下、より好ましくは0.0010%以下である。一方で、Bi含有量の下限値は、特に制限されず、0%であればよい。ただ、Biは、磁束密度を向上させる効果を有するので、Bi含有量は、0%超としてもよく、0.00050%以上としてもよい。
B(ボロン)は、母材鋼板にとって選択元素である。B含有量が0.080%を超えると、磁束密度のばらつき(標準偏差)が大きくなることがある。そのため、B含有量は0.080%以下であればよい。Bi含有量は、好ましくは0.070%以下、より好ましくは0.060%以下である。一方で、B含有量の下限値は、特に制限されず、0%であればよい。ただ、Bは、窒化物を形成して二次再結晶時のインヒビターとしての効果を有するので、B含有量は、0%超としてもよく、0.00050%以上としてもよい。
P(燐)は、母材鋼板にとって選択元素である。P含有量が0.50%を超えれば、鋼板の加工性が顕著に低下することがある。そのため、母材鋼板のP含有量は0.50%以下であればよい。P含有量は、好ましくは0.30%以下、より好ましくは0.10%以下である。一方で、P含有量の下限値は、特に制限されず、0%であればよい。ただ、Pは、集合組織を改善し、鋼板の磁気特性を改善する効果を有するので、P含有量を、0%超としてもよく、0.0020%以上としてもよい。
Ti(チタン)は、母材鋼板にとって選択元素である。Ti含有量が0.0150%を超えれば、磁気特性がに低下することがある。そのため、母材鋼板のTi含有量は0.0150%以下であればよい。Ti含有量は、好ましくは0.0130%以下、より好ましくは0.010%以下である。一方で、Ti含有量の下限値は、特に制限されず、0%であればよい。ただ、Tiは、炭化物や窒化物や炭窒化物を形成して二次再結晶時のインヒビターとしての効果を有するので、Ti含有量を、0%超としてもよく、0.0020%以上としてもよい。
Sn(スズ)は、母材鋼板にとって選択元素である。Sn含有量が0.10%を超えると、二次再結晶が不安定となり、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のSn含有量は0.10%以下であればよい。Sn含有量は、好ましくは0.090%以下、より好ましくは0.080%以下である。一方で、Sn含有量の下限値は、特に制限されず、0%であればよい。ただ、Snは、Goss方位の集積度を高めて、磁気特性を改善させる効果を有するので、Sn含有量は、0%超としてもよく、0.0050%以上としてもよい。
Sb(アンチモン)は、母材鋼板にとって選択元素である。Sb含有量が0.10%を超えると、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のSb含有量は0.10%以下であればよい。Sb含有量は、好ましくは0.090%以下、より好ましくは0.080%以下である。一方で、Sb含有量の下限値は、特に制限されず、0%であればよい。ただ、Sbは、インヒビターとして機能して二次再結晶を安定化する効果を有するので、Sb含有量は、0%超としてもよく、0.010%以上としてもよい。
Cr(クロム)は、母材鋼板にとって選択元素である。Cr含有量が0.30%を超えると、Cr酸化物を形成し、磁気特性に悪影響を及ぼすことがある。そのため、母材鋼板のCr含有量は0.30%以下であればよい。Cr含有量は、好ましくは0.20%以下、より好ましくは0.10%以下である。一方で、Cr含有量の下限値は、特に制限されず、0%であればよい。ただ、Crは、Goss方位の集積度を高めて、磁気特性を改善させる効果を有するので、Cr含有量は、0%超としてもよく、0.010%以上としてもよい。
Ni(ニッケル)は、母材鋼板にとって選択元素である。Ni含有量が1.0%を超えると、二次再結晶が不安定になることがある。そのため、母材鋼板のNi含有量は1.0%以下であればよい。Ni含有量は、好ましくは0.20%以下、より好ましくは0.10%以下である。一方で、Ni含有量の下限値は、特に制限されず、0%であればよい。ただ、Niは、電気抵抗を高めて鉄損を低減する効果を有するので、Ni含有量は、0%超としてもよく、0.010%以上としてもよい。
鋳造工程では、スラブを準備する。スラブの製造方法の一例は次のとおりである。溶鋼を製造(溶製)する。溶鋼を用いてスラブを製造する。連続鋳造法によりスラブを製造してもよい。溶鋼を用いてインゴットを製造し、インゴットを分塊圧延してスラブを製造してもよい。スラブの厚さは、特に限定されない。スラブの厚さは、たとえば、150~350mmである。スラブの厚さは、好ましくは、220~280mmである。スラブとして、厚さが10~70mmの、いわゆる薄スラブを用いてもよい。薄スラブを用いる場合、熱間圧延工程において、仕上げ圧延前の粗圧延を省略できる。
炭素(C)は、製造工程においては一次再結晶組織の制御に有効な元素であるものの、最終製品への含有量が過剰であると磁気特性に悪影響を及ぼす。したがって、C含有量は0.085%以下である。C含有量の好ましい上限は0.075%である。Cは脱炭焼鈍工程及び仕上げ焼鈍工程で純化され、0.005%以下となる。Cを含む場合、工業生産における生産性を考慮すると、C含有量の下限は0%超であってもよく、0.001%であってもよい。
シリコン(Si)は、方向性電磁鋼板の電気抵抗を高めて鉄損を低下させる。Si含有量が2.0%未満であれば、仕上げ焼鈍時にγ変態が生じて、方向性電磁鋼板の結晶方位が損なわれてしまう。一方、Si含有量が7.0%を超えれば、冷間加工性が低下して、冷間圧延時に割れが発生しやすくなる。Si含有量の好ましい下限は2.5%であり、さらに好ましくは3.0%である。Si含有量の好ましい上限は4.5%であり、さらに好ましくは4.0%である。
マンガン(Mn)はS又はSeと結合して、MnS、又は、MnSeを生成し、インヒビターとして機能する。Mnを含有させる場合、Mn含有量が0.05~1.00%の範囲内にある場合に、二次再結晶が安定する。なお、インヒビターの機能の一部をNb群元素の窒化物によって担うことが可能である。この場合は、一般的なインヒビターとしてのMnS、又は、MnSe強度は弱めに制御する。このため、Mn含有量の好ましい上限は0.50%であり、さらに好ましくは0.20%である。
硫黄(S)及びセレン(Se)は、Mnと結合して、MnS又はMnSeを生成し、インヒビターとして機能する。S及びSeの少なくとも一方を含有させる場合、S及びSeの含有量が合計で0.003~0.035%であれば、二次再結晶が安定する。なお、インヒビターの機能の一部をNb群元素の窒化物によって担うことが可能である。この場合は、一般的なインヒビターとしてのMnS、又は、MnSe強度は弱めに制御する。このため、S及びSe含有量の合計の好ましい上限は0.025%であり、さらに好ましくは0.010%である。S及びSeは仕上げ焼鈍後に残留すると化合物を形成し、鉄損を劣化させる。そのため、仕上げ焼鈍中の純化により、S及びSeをできるだけ少なくすることが好ましい。
アルミニウム(Al)は、Nと結合して(Al、Si)Nとして析出し、インヒビターとして機能する。Alを含有させる場合、Al含有量が0.010~0.065%の範囲内にある場合に、後述の窒化により形成されるインヒビターとしてのAlNは二次再結晶温度域を拡大し、特に高温域での二次再結晶が安定する。したがって、Al含有量は0.010~0.065%である。Al含有量の好ましい下限は0.020%であり、さらに好ましくは0.025%である。二次再結晶の安定性の観点から、Al含有量の好ましい上限は0.040%であり、さらに好ましくは0.035%である。
窒素(N)は、Alと結合してインヒビターとして機能する。Nは製造工程の途中で窒化により含有させることが可能であるため下限は規定しない。例えば、N含有量の下限は0%超であってもよく、0.001%であってもよい。一方、Nを含有させる場合、N含有量が0.012%を超えれば、鋼板中に欠陥の一種であるブリスタが発生しやすくなる。N含有量の好ましい上限は0.010%であり、さらに好ましくは0.009%である。Nは仕上げ焼鈍工程で純化され、仕上げ焼鈍工程後には0.005%以下となる。
Nb群元素(Nb、V、Mo、Ta、及びWの1種以上)の合計含有量は0.050%以下であればよい。Nb群元素をインヒビターの一部として活用する場合、Nb群元素の合計含有量が0.030%以下であると、適切なタイミングで二次再結晶を開始させるので好ましい。また、発生する二次再結晶粒の方位が非常に好ましいものとなり、最終的に磁気特性にとって好ましい組織に制御できる。特に、Nb及びTaはその効果が強く好ましい。Nb群元素の合計含有量は下限値を設ける必要がなく、下限値が0%でもよい。この下限値は、0.003%であることが好ましい。
Cu:0.40%以下、
Bi:0.010%以下、
B:0.080%以下、
P:0.50%以下、
Ti:0.015%以下、
Sn:0.10%以下、
Sb:0.10%以下、
Cr:0.30%以下、
Ni:1.00%以下
の少なくとも1種を含有してもよい。
これら任意元素は、公知の目的に応じて含有させればよいため、任意元素の含有量の下限値を設ける必要はなく、下限値が0%でもよい。
熱間圧延工程は、所定の温度(例えば1100~1400℃)に加熱されたスラブの熱間圧延を行い、熱延鋼板を得る工程である。熱間圧延工程では、例えば、加熱工程で加熱された珪素鋼素材(スラブ)の粗圧延を行った後、仕上げ圧延を行って所定厚さ、例えば、1.8~3.5mmの熱延鋼板とする。仕上げ圧延終了後、熱延鋼板を所定の温度で巻き取る。
熱延板焼鈍工程は、熱間圧延工程で得た熱延鋼板を所定の温度条件(例えば750~1200℃で30秒間~10分間)で焼鈍して、焼鈍鋼板を得る工程である。熱延板焼鈍は、一般的に、熱間圧延工程後の熱延鋼板を焼鈍することにより、再結晶率や残存歪や結晶粒径などの鋼板組織を制御し、また鋼中の析出物形態を好ましく調整するために実施される。例えば、高温スラブ加熱プロセスにおいては、AlNなどの析出物の形態を最終的に制御する工程であり、均一かつ微細に析出するように条件調整する。熱延板焼鈍として、例えば、鋼板を1050℃~1150℃に加熱した後、AlNなどを適正に析出させるため、50~150秒かけて中間温度(850℃~950℃)まで緩冷却した後、水冷却してもよい。
冷間圧延工程は、熱延板焼鈍工程で得た焼鈍鋼板を、1回の冷間圧延、又は焼鈍(中間焼鈍)を介して複数回(2回以上)の冷間圧延(例えば総冷延率で80~95%)により、例えば、0.10~0.50mmの厚さを有する冷延鋼板を得る工程である。磁気特性を改善するために、例えば、冷間圧延のパス間温度を100℃~300℃程度にしてもよい。
本実施形態では、冷間圧延工程後の冷延鋼板に対して、局所加熱領域を形成するための局所急速加熱を行う。急速加熱方法としては、鋼板を局所的に加熱できるものであればよく、特に限定しない。例えば、鋼板の表裏面にスポット電極を接触させて鋼板内に電流を通電して加熱する方法、レーザー光や電子ビームなどを鋼板表面に照射して加熱する方法、誘導加熱によって局所的に加熱する方法、熱片を接触させて加熱する方法などを採用することができる。個々の局所加熱領域の大きさとしては、直径が10μm~10mm程度の点状領域、あるいは幅が10μm~10mm程度の線状領域とすることができる。また、通電加熱に用いる電極は、上記のように円形状の電極としてもよく、または線状の電極としてもよい。
脱炭焼鈍工程では、局所急速加熱工程後の冷延鋼板に対して、脱炭焼鈍(一次焼鈍)を行う。この脱炭焼鈍により、局所加熱影響領域に形成されるゴス方位粒の存在頻度が増大し、ゴス方位粒の粒径が増大し、理想ゴス方位に近い方位を持つ粗大ゴス方位粒が好ましく形成される。脱炭焼鈍条件としては、加熱速度を10~10000℃/秒、焼鈍温度を700~900℃、焼鈍時間を10~600秒とすればよい。また、冷延鋼板に脱炭焼鈍を行うことで、冷延鋼板中に含まれるCが除去される。脱炭焼鈍は、冷延鋼板中に含まれる「C」を除去するために、湿潤雰囲気中で行うことが好ましい。
窒化処理は、スラブ加熱温度が1280℃以下の低温スラブ加熱プロセスで有効な処理であり、二次再結晶におけるインヒビターの強度を調整するために重要な工程である。窒化処理は、脱炭処理の開始から、仕上げ焼鈍における二次再結晶の開始までの間に、鋼板の窒素量を40~200ppm程度増加させる。窒化処理としては、例えば、アンモニア等の窒化能のあるガスを含有する雰囲気中で焼鈍する処理、MnN等の窒化能を有する粉末を含む焼鈍分離剤を塗布した脱炭焼鈍鋼板を仕上げ焼鈍する処理等が例示される。窒化処理後の窒化量は130~350ppmとすることが好ましく、さらには150~250ppmとすることが好ましい。
焼鈍分離剤塗布工程は、脱炭焼鈍鋼板に焼鈍分離剤を塗布する工程である。焼鈍分離剤としては、例えば、MgOを主成分とする焼鈍分離剤やAl2O3を主成分とする焼鈍分離剤を用いることができる。焼鈍分離剤を塗布後の脱炭焼鈍鋼板は、コイル状に巻取った状態で、次の仕上げ焼鈍工程で仕上げ焼鈍される。
仕上げ焼鈍工程は、焼鈍分離剤が塗布された脱炭焼鈍鋼板に仕上げ焼鈍(二次焼鈍)を施し、二次再結晶を生じさせる工程である。この工程は、一次再結晶粒の成長をインヒビターにより抑制した状態で二次再結晶を進行させることによって、{100}<001>方位粒を優先成長させ、磁束密度を飛躍的に向上させる。
仕上げ焼鈍後の鋼板に、りん酸あるいはりん酸塩、無水クロム酸あるいはクロム酸塩およびコロイド状シリカを含むコーティング溶液を塗布して焼き付けて(例えば、350℃~1150℃で5~300秒間)、絶縁被膜を形成する。
ρ:空気の密度(kg/m3)
c:音速(m/秒)
P0:1kHzの音を人間が聞き取ることのできる最小の圧力(Pa)、
fi:周波数(Hz)
λ(fi):フーリエ変換した周波数ごとの磁歪量
α(fi):周波数fiのA特性
π:円周率
ρ=1.185(kg/m3)
c=346.3(m/秒)
P0=2×10-5(Pa)
2 局所加熱影響領域
3 局所加熱非影響領域(マトリックス部)
4 局所加熱領域境界
5 局所加熱影響領域境界
14 ゴス方位粒
15 粗大ゴス方位粒
21 圧延方向
22 幅方向(圧延直角方向)
Claims (1)
- 方向性電磁鋼板であって、
圧延面法線方向Zを回転軸とする理想ゴス方位からのずれ角をαと定義し、
圧延直角方向Cを回転軸とする理想ゴス方位からのずれ角をβと定義し、
圧延方向Lを回転軸とする理想ゴス方位からのずれ角をγと定義し、
板面上の1つの測定点で測定する結晶方位のずれ角を(α β γ)と表し、
前記1つの測定点における角度偏差をφ=(α2+β2)1/2と定義し、
圧延方向Lに沿って間隔が1mmの複数の測定点で求めた角度偏差φの平均値をaveφLと定義したとき、
前記aveφLが、aveφL≦3.5°を満たし、
前記板面上で隣接し且つ間隔が1mmである2つの測定点で測定する結晶方位のずれ角を(α1 β1 γ1)および(α2 β2 γ2)と表し、
[(α2-α1)2+(β2-β1)2+(γ2-γ1)2]1/2≧1.0°を満足する2つの測定点の中間点を粒界GBと定義し、
前記粒界GBに基づいて求める圧延方向Lの粒径を単位mmでDLと定義し、
圧延方向Lに沿って求めた粒径DLを大きい順に並べて大きい方から個数基準で10%となる粒径を単位mmでDL10と定義したとき、
前記DL10が、DL10≦100-15×aveφLを満たし、
前記粒界GBに基づいて求める圧延直角方向Cの粒径を単位mmでDCと定義し、
圧延直角方向Cに沿って求めた粒径DCの平均値をaveDCと定義したとき、
前記aveDCが、aveDC≧50を満たす
ことを特徴とする方向性電磁鋼板。
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| KR1020257042255A KR20260013964A (ko) | 2023-06-29 | 2024-06-27 | 방향성 전자 강판 |
| JP2024556104A JP7606155B1 (ja) | 2023-06-29 | 2024-06-27 | 方向性電磁鋼板 |
| EP24832026.9A EP4737606A1 (en) | 2023-06-29 | 2024-06-27 | Grain-oriented electrical steel sheet |
| CN202480042479.7A CN121399283A (zh) | 2023-06-29 | 2024-06-27 | 方向性电磁钢板 |
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| JP2023106860 | 2023-06-29 | ||
| JP2023-106860 | 2023-06-29 |
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| EP (1) | EP4737606A1 (ja) |
| JP (1) | JP7606155B1 (ja) |
| KR (1) | KR20260013964A (ja) |
| CN (1) | CN121399283A (ja) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2026005045A1 (ja) * | 2024-06-27 | 2026-01-02 | 日本製鉄株式会社 | 電磁鋼板用金属板の加熱装置と加熱方法、及び電磁鋼板の製造方法 |
| WO2026005032A1 (ja) * | 2024-06-27 | 2026-01-02 | 日本製鉄株式会社 | 電磁鋼板用金属板の通電加熱装置と通電加熱方法、及び電磁鋼板の製造方法 |
| EP4653555A4 (en) * | 2023-01-18 | 2026-06-03 | Nippon Steel Corp | GRAIN-ORIENTED ELECTROMAGNETIC STEEL SHEET MANUFACTURING PROCESS |
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| JPS572839A (en) | 1980-06-04 | 1982-01-08 | Nippon Steel Corp | Production of unidirectional silicon steel plate of high magnetic flux density |
| JPS61190017A (ja) | 1985-02-20 | 1986-08-23 | Nippon Steel Corp | 鉄損の低い一方向性珪素鋼板の製造方法 |
| JP2001294996A (ja) | 2000-04-06 | 2001-10-26 | Nippon Steel Corp | 高加工性方向性電磁鋼板およびその製造方法 |
| JP2005240102A (ja) | 2004-02-26 | 2005-09-08 | Jfe Steel Kk | 鉄損特性に優れた方向性電磁鋼板 |
| JP2015206114A (ja) | 2014-04-11 | 2015-11-19 | 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 |
| JP2021181604A (ja) * | 2020-05-20 | 2021-11-25 | 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 |
| JP2021183722A (ja) * | 2020-05-20 | 2021-12-02 | Jfeスチール株式会社 | 方向性電磁鋼板とその製造方法ならびに歪導入装置 |
| JP2023106860A (ja) | 2022-01-21 | 2023-08-02 | 味の素株式会社 | 封止用組成物およびその製造方法、並びに封止用シート |
-
2024
- 2024-06-27 JP JP2024556104A patent/JP7606155B1/ja active Active
- 2024-06-27 KR KR1020257042255A patent/KR20260013964A/ko active Pending
- 2024-06-27 EP EP24832026.9A patent/EP4737606A1/en active Pending
- 2024-06-27 WO PCT/JP2024/023282 patent/WO2025005167A1/ja not_active Ceased
- 2024-06-27 CN CN202480042479.7A patent/CN121399283A/zh active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS572839A (en) | 1980-06-04 | 1982-01-08 | Nippon Steel Corp | Production of unidirectional silicon steel plate of high magnetic flux density |
| JPS61190017A (ja) | 1985-02-20 | 1986-08-23 | Nippon Steel Corp | 鉄損の低い一方向性珪素鋼板の製造方法 |
| JP2001294996A (ja) | 2000-04-06 | 2001-10-26 | Nippon Steel Corp | 高加工性方向性電磁鋼板およびその製造方法 |
| JP2005240102A (ja) | 2004-02-26 | 2005-09-08 | Jfe Steel Kk | 鉄損特性に優れた方向性電磁鋼板 |
| JP2015206114A (ja) | 2014-04-11 | 2015-11-19 | 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 |
| JP2021181604A (ja) * | 2020-05-20 | 2021-11-25 | 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 |
| JP2021183722A (ja) * | 2020-05-20 | 2021-12-02 | Jfeスチール株式会社 | 方向性電磁鋼板とその製造方法ならびに歪導入装置 |
| JP2023106860A (ja) | 2022-01-21 | 2023-08-02 | 味の素株式会社 | 封止用組成物およびその製造方法、並びに封止用シート |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4653555A4 (en) * | 2023-01-18 | 2026-06-03 | Nippon Steel Corp | GRAIN-ORIENTED ELECTROMAGNETIC STEEL SHEET MANUFACTURING PROCESS |
| WO2026005045A1 (ja) * | 2024-06-27 | 2026-01-02 | 日本製鉄株式会社 | 電磁鋼板用金属板の加熱装置と加熱方法、及び電磁鋼板の製造方法 |
| WO2026005032A1 (ja) * | 2024-06-27 | 2026-01-02 | 日本製鉄株式会社 | 電磁鋼板用金属板の通電加熱装置と通電加熱方法、及び電磁鋼板の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20260013964A (ko) | 2026-01-29 |
| JPWO2025005167A1 (ja) | 2025-01-02 |
| JP7606155B1 (ja) | 2024-12-25 |
| EP4737606A1 (en) | 2026-05-06 |
| CN121399283A (zh) | 2026-01-23 |
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