WO2020149336A1 - 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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- WO2020149336A1 WO2020149336A1 PCT/JP2020/001175 JP2020001175W WO2020149336A1 WO 2020149336 A1 WO2020149336 A1 WO 2020149336A1 JP 2020001175 W JP2020001175 W JP 2020001175W WO 2020149336 A1 WO2020149336 A1 WO 2020149336A1
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Definitions
- the present invention relates to a method for manufacturing a grain-oriented electrical steel sheet.
- the present application claims priority based on Japanese Patent Application No. 2019-005085 filed in Japan on January 16, 2019, the contents of which are incorporated herein by reference.
- Oriented electrical steel sheets are mainly used for transformers.
- the transformer is continuously excited for a long period of time from being installed to being discarded, and continues to generate energy loss.Therefore, energy loss when magnetized by alternating current, that is, iron loss, It is the main indicator that determines performance.
- a coating is usually formed on the surface of the grain-oriented electrical steel sheet for the purpose of reducing iron loss. This coating reduces the iron loss as a single steel plate by applying tension to the grain-oriented electrical steel plate. This coating further reduces the iron loss as an iron core by ensuring electrical insulation between the steel sheets when the grain-oriented electrical steel sheets are laminated and used.
- a forsterite coating which is an oxide coating containing Mg, was formed on the surface of the mother steel sheet, and an insulating coating was further formed on the surface of the forsterite coating.
- the coating on the mother steel plate includes the forsterite coating and the insulating coating.
- Each of the forsterite coating and the insulating coating has both an insulating function and a function of applying a tension to the mother steel sheet.
- the forsterite coating which is an oxide coating containing Mg, is formed on the mother steel sheet during decarburization annealing with an annealing separator containing magnesia (MgO) as a main component in the final annealing that causes secondary recrystallization in the steel sheet.
- MgO magnesia
- silicon oxide (SiO 2 ) react with each other during the heat treatment performed at 900 to 1200° C. for 30 hours or more.
- the insulating coating is applied to the mother steel sheet after finish annealing with a coating solution containing, for example, phosphoric acid or phosphate, colloidal silica, and chromic anhydride or chromate, and the temperature is 300 to 950° C. for 10 seconds. It is formed by baking and drying as described above.
- the above adhesion has been secured mainly by the anchor effect due to the unevenness of the interface between the mother steel plate and the forsterite coating.
- the unevenness of the interface also hinders the movement of the magnetic domain wall when the grain-oriented electrical steel sheet is magnetized, and thus is also a factor that hinders the reduction of iron loss.
- Patent Document 1 JP-A-49-096920 (Patent Document 1) and WO 2002/088403 (Patent Document 2).
- the forsterite film is removed by pickling or the like, and the surface of the mother steel sheet is smoothed by chemical polishing or electrolytic polishing.
- an annealing separator containing alumina Al 2 O 3 is used at the time of finish annealing to suppress the formation of the forsterite coating itself, and Smooth it.
- the present invention has been made in view of the above problems. It is an object of the present invention to provide a method for producing a grain-oriented electrical steel sheet having no forsterite coating and having excellent magnetic properties (especially iron loss) and coating adhesion.
- the present inventors presuppose that an insulating coating is formed on the surface of a steel sheet for grain-oriented electrical steel sheets in which a forsterite coating is not generated for the purpose of reducing iron loss, and the steel sheet surface is smoothed.
- a method for improving the adhesion (coating adhesion) with the insulating coating was examined.
- a method for manufacturing a grain-oriented electrical steel sheet according to an aspect of the present invention is As a chemical composition, in mass%, C: 0.030 to 0.100%, Si: 0.80 to 7.00%, Mn: 0.01 to 1.00%, Sum of S and Se: 0 to 0.060%, Acid soluble Al: 0.010 to 0.065%, N: 0.004 to 0.012%, Cr: 0 to 0.30%, Cu: 0 to 0.40%, P: 0 to 0.50%, Sn: 0 to 0.30%, Sb: 0 to 0.30%, Ni: 0 to 1.00%, B: 0 to 0.008%, V: 0 to 0.15%, Nb: 0 to 0.20%, Mo: 0 to 0.10%, Ti: 0 to 0.015%, Bi: 0 to 0.010%, A hot rolling step of hot rolling a steel slab with the balance being Fe and impurities to obtain a hot rolled steel sheet; A cold rolling step of
- the holding is performed for 10 to 600 seconds
- the annealing separator applying step Wherein annealing in the separating agent, the MgO and the Al 2 O 3 MgO / the mass ratio of (MgO + Al 2 O 3) 5-50%, the hydration water is 1.5 wt% or less
- the finish annealing step The decarburized annealing plate coated with the annealing separator is kept at a temperature of 1100 to 1200° C. for 10 hours or more in a mixed gas atmosphere containing 50% or more by volume of hydrogen.
- Excessive annealing separator is removed from the surface of the finish annealed plate by washing with water using a solution containing an inhibitor which is at least one of triethanolamine, rosinamine or mecaptan, and the amount of iron-based hydroxide on the surface of the steel plate.
- the amount of iron-based oxide per surface is 0.9 g/m 2 or less.
- the surface of the finish-annealed plate from which the surplus annealing separator has been removed by chemical polishing has an average roughness Ra of 0.1 ⁇ m or less.
- the insulating film forming step A film-forming solution containing a phosphate, colloidal silica, and crystalline phosphide, coated, baked at 350 to 1150° C., and cooled, but containing no crystalline phosphide and colloidal silica. Is applied and baked at 350 to 1150° C. to form an insulating film.
- a hot-rolled sheet annealing step of annealing the hot-rolled steel sheet or pickling is performed between the hot-rolling step and the cold-rolling step. You may provide at least 1 of the hot-rolled board pickling process to perform.
- a nitriding treatment is performed to anneal the cold rolled steel sheet in an atmosphere containing ammonia. Good.
- the decarburization annealing step and the annealing are performed between the cold rolling step and the decarburizing annealing step.
- a magnetic domain control step of performing a magnetic domain control process may be provided either during the separating agent application step, between the smoothing step and the insulating film forming step, or after the insulating film forming step.
- an acidic solution having a volume ratio concentration of less than 20% after the washing with water You may perform pickling using.
- the steel slab has a chemical composition of mass%, Cr: 0.02 to 0.30%, Cu: 0.05 to 0.40%, P: 0.005-0.50%, Sn: 0.02 to 0.30%, Sb: 0.01 to 0.30%, Ni: 0.01 to 1.00%, B: 0.0005 to 0.008%, V: 0.002-0.15%, Nb: 0.005 to 0.20%, Mo: 0.005 to 0.10%, Ti: 0.002 to 0.015%, and Bi: 0.001 to 0.010%, You may contain at least 1 sort(s) selected from the group which consists of.
- a method for manufacturing a grain-oriented electrical steel sheet according to an embodiment of the present invention is a method for manufacturing a grain-oriented electrical steel sheet having no forsterite coating.
- the manufacturing method includes the following steps. (I) Hot rolling step of hot rolling a steel slab having a predetermined chemical composition to obtain a hot rolled steel sheet. (ii) Cold rolling the hot rolled steel sheet once or twice with intermediate annealing.
- the method for manufacturing a grain-oriented electrical steel sheet according to this embodiment may further include the following steps.
- the chemical composition, in mass % is C: 0.030 to 0.100%, Si: 0.80 to 7.00%, Mn: 0.01 to 1.00%, and the sum of S+Se: 0 to 0.060%, acid-soluble Al: 0.010 to 0.065%, N: 0.004 to 0.012%, Cr: 0 to 0.30%, Cu: 0 to 0.40%, P : 0 to 0.50%, Sn: 0 to 0.30%, Sb: 0 to 0.30%, Ni: 0 to 1.00%, B: 0 to 0.008%, V: 0 to 0.
- the billet is hot rolled to obtain a hot rolled steel sheet.
- the steel sheet after the hot rolling process is referred to as a hot rolled steel sheet.
- the steel slab used in the hot rolling process.
- molten steel having a predetermined chemical composition may be melted, and the slab may be manufactured using the molten steel.
- the slab may be manufactured by a continuous casting method, an ingot may be manufactured using molten steel, and the slab may be manufactured by slab-rolling the ingot. Also, the slab may be manufactured by other methods.
- the thickness of the slab is not particularly limited, but is, for example, 150 to 350 mm.
- the thickness of the slab is preferably 220-280 mm.
- a so-called thin slab having a thickness of 10 to 70 mm may be used as the slab.
- % related to chemical composition means% by mass.
- C is an element effective in controlling the primary recrystallization structure, but has an adverse effect on the magnetic properties, and is an element removed by decarburization annealing before finish annealing. If the C content of the steel slab exceeds 0.100%, the decarburization annealing time becomes long and the productivity is reduced. Therefore, the C content is 0.100% or less. It is preferably 0.085% or less, more preferably 0.070% or less.
- Si increases the electrical resistance of the grain-oriented electrical steel sheet and reduces the iron loss. If the Si content is less than 0.80%, ⁇ transformation occurs during finish annealing, and the crystal orientation of the grain-oriented electrical steel sheet is impaired. Therefore, the Si content is 0.80% or more.
- the Si content is preferably 2.00% or more, more preferably 2.50% or more.
- the Si content exceeds 7.00%, the cold workability is deteriorated and cracks are likely to occur during cold rolling. Therefore, the Si content is 7.00% or less.
- the Si content is preferably 4.50% or less, more preferably 4.00% or less.
- Mn 0.01 to 1.00%
- Manganese (Mn) increases the electrical resistance of the grain-oriented electrical steel sheet and reduces the iron loss. Further, Mn combines with S or Se to generate MnS or MnSe, and functions as an inhibitor. The secondary recrystallization is stable when the Mn content is in the range of 0.01 to 1.00%. Therefore, the Mn content is 0.01 to 1.00%.
- the preferable lower limit of the Mn content is 0.08%, more preferably 0.09%.
- the preferable upper limit of the Mn content is 0.50%, more preferably 0.20%.
- S (sulfur) and Se (selenium) are elements that combine with Mn to form MnS and/or MnSe that function as an inhibitor. If the sum (S+Se) of either or both of S and Se is more than 0.060%, the precipitation dispersion of MnS and MnSe becomes nonuniform after hot rolling. In this case, the desired secondary recrystallized structure cannot be obtained, the magnetic flux density is lowered, or MnS remains in the steel after purification, and the hysteresis loss is deteriorated. Therefore, the total content of S and Se is set to 0.060% or less.
- the lower limit of the total content of S and Se is not particularly limited and may be 0%. This lower limit may be 0.003% or more. When used as an inhibitor, it is preferably 0.015% or more.
- Acid-soluble Al (Sol. Al) 0.010 to 0.065%
- Acid-soluble Al (aluminum) (Sol. Al) is an element that combines with N to generate AlN or (Al, Si)N that functions as an inhibitor. If the amount of acid-soluble Al is less than 0.010%, the effect is not sufficiently exhibited and the secondary recrystallization does not proceed sufficiently. Therefore, the acid-soluble Al content is set to 0.010% or more.
- the acid-soluble Al content is preferably 0.015% or more, more preferably 0.020% or more.
- the acid-soluble Al (Sol. Al) is 0.065% or less.
- the acid-soluble Al content is preferably 0.055% or less, more preferably 0.050% or less.
- N nitrogen
- nitrogen is an element that combines with Al to form AlN or (Al, Si)N that functions as an inhibitor. If the N content is less than 0.004%, the formation of AlN or (Al,Si)N is insufficient, so N is made 0.004% or more. It is preferably 0.006% or more, more preferably 0.007% or more. On the other hand, if the N content is more than 0.012%, there is a concern that blisters (holes) may be formed in the steel sheet. Therefore, the N content is set to 0.012% or less.
- the chemical composition of the above steel slab contains the above elements and the balance consists of Fe and impurities.
- one or more selected elements may be contained in the following range instead of part of Fe.
- the selective element contained in place of part of Fe include Cr, Cu, P, Sn, Sb, Ni, B, V, Nb, Mo, Ti, and Bi.
- the selective element since the selective element may not be included, the lower limit thereof is 0%. Even if these selective elements are contained as impurities, the above effects are not impaired.
- the "impurities” refer to those that are mixed from ore or scrap as a raw material, or from the manufacturing environment or the like when industrially manufacturing steel.
- Cr chromium
- the Cr content is preferably 0.02% or more, more preferably 0.05% or more.
- the upper limit of the Cr content is preferably 0.30%, and is preferably 0.20%. It is more preferably 0.12% and even more preferably 0.12%.
- Cu (copper) is also an element effective in increasing the electric resistance and reducing the iron loss. Therefore, Cu may be contained.
- the Cu content is preferably 0.05% or more, and more preferably 0.10% or more.
- the upper limit of the Cu content is preferably 0.40%, more preferably 0.30%, and further preferably 0.20%.
- P 0 to 0.50%
- P phosphorus
- the P content is preferably 0.005% or more, and more preferably 0.010% or more.
- the upper limit of the P content is preferably 0.50%, more preferably 0.20%, and further preferably 0.15%.
- Sn (tin) and Sb (antimony) are elements effective in stabilizing the secondary recrystallization and developing the ⁇ 110 ⁇ 001> orientation. Therefore, Sn or Sb may be contained.
- the Sn content is preferably 0.02% or more, and more preferably 0.05% or more.
- the Sb content is preferably 0.01% or more, more preferably 0.03% or more.
- the magnetic properties may be adversely affected. Therefore, it is preferable to set the upper limits of the Sn content and the Sb content to 0.30%, respectively.
- the upper limit of the Sn content is more preferably 0.15%, further preferably 0.10%.
- the upper limit of the Sb content is more preferably 0.15%, further preferably 0.10%.
- Ni nickel
- Ni nickel
- the Ni content is preferably 0.01% or more, more preferably 0.02% or more.
- the Ni content is preferably 1.00% or less, more preferably 0.20% or less, and further preferably 0.10% or less.
- B (boron) is an element effective in forming BN which combines with N to exert an inhibitory effect. Therefore, B may be contained.
- the B content is preferably 0.0005% or more, more preferably 0.0010% or more.
- the upper limit of the B content is preferably 0.008%, more preferably 0.005%, and further preferably 0.003%.
- V vanadium
- Nb niobium
- Ti titanium
- V, Nb, or Ti may be contained.
- the V content is preferably 0.002% or more, and more preferably 0.010% or more.
- the Nb content is preferably 0.005% or more, more preferably 0.020% or more.
- the Ti content is preferably 0.002% or more, more preferably 0.004% or more.
- the steel slab contains V in a range of more than 0.15%, Nb in a range of more than 0.20%, and Ti in a range of more than 0.015%, these elements remain in the final product and V
- the content may exceed 0.15%, the Nb content may exceed 0.20%, or the Ti content may exceed 0.015%.
- the magnetic properties of the final product may deteriorate. Therefore, the upper limit of the V content is preferably 0.15%, more preferably 0.10%, and further preferably 0.05%.
- the upper limit of the Ti content is preferably 0.015%, more preferably 0.010%, and further preferably 0.008%.
- the upper limit of the Nb content is preferably 0.20%, more preferably 0.10%, and further preferably 0.08%.
- Mo mobdenum
- Mo mobdenum
- the Mo content is preferably 0.005% or more, more preferably 0.01% or more.
- the upper limit of the Mo content is preferably 0.10%, more preferably 0.08%, and further preferably 0.05%.
- Bi bismuth
- the Bi content is preferably 0.001% or more, and more preferably 0.002% or more.
- the upper limit of the Bi content is preferably 0.010%, more preferably 0.008%, and further preferably 0.006%.
- the above chemical composition may be measured by a general steel analysis method.
- the chemical composition may be measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry).
- sol. Al may be measured by ICP-AES using a filtrate obtained by thermally decomposing a sample with an acid.
- C and S may be measured by a combustion-infrared absorption method
- N may be measured by an inert gas melting-thermal conductivity method
- O may be measured by an inert gas melting-non-dispersion infrared absorption method.
- the hot rolling conditions are not particularly limited. For example, the following conditions are set.
- the slab is heated prior to hot rolling.
- the slab is charged into a known heating furnace or a known soaking furnace and heated.
- One way is to heat the slab below 1280°C.
- the lower limit of the heating temperature of the slab is not particularly limited. If the heating temperature is too low, hot rolling may become difficult and productivity may be reduced. Therefore, the heating temperature may be set in the range of 1280° C. or lower in consideration of productivity.
- the preferable lower limit of the heating temperature of the slab is 1100°C.
- the preferable upper limit of the heating temperature of the slab is 1250°C.
- the slab is heated to a high temperature of 1320° C. or higher.
- a high temperature of 1320° C. or higher AlN and Mn(S, Se) are dissolved, and fine precipitation is performed in the subsequent steps, whereby secondary recrystallization can be stably exhibited. It is possible to omit the slab heating step itself and start hot rolling after casting until the temperature of the slab falls.
- the hot rolling mill includes, for example, a rough rolling mill and a finish rolling mill arranged downstream of the rough rolling mill.
- the rough rolling mill includes a row of rough rolling stands. Each rough rolling stand includes a plurality of rolls arranged one above the other.
- the finish rolling mill also includes a finish rolling stand arranged in a line. Each finish rolling stand includes a plurality of rolls arranged one above the other.
- the finishing temperature in the hot rolling process (the temperature of the steel sheet at the exit side of the finish rolling stand for finally rolling the steel sheet in the finish rolling mill) is, for example, 700 to 1150°C.
- a hot rolled steel sheet is manufactured by the above hot rolling process.
- the hot-rolled steel sheet obtained in the hot-rolling step is annealed (hot-rolled sheet annealing) to obtain a hot-rolled annealed sheet.
- the steel sheet after the hot rolled sheet annealing step is referred to as a hot rolled annealed sheet.
- the hot-rolled sheet annealing is performed for the purpose of making the non-uniform structure generated during hot rolling as uniform as possible, controlling the precipitation of AlN that is an inhibitor (fine precipitation), and controlling the second phase/solid solution carbon. ..
- Known annealing conditions may be selected according to the purpose. For example, when homogenizing a non-uniform structure generated during hot rolling, the hot rolled steel sheet is held at an annealing temperature (furnace temperature in a hot rolling sheet annealing furnace) of 750 to 1200° C. for 30 to 600 seconds. It is not always necessary to anneal the hot-rolled sheet, and whether or not to carry out the hot-rolled sheet anneal step may be determined according to the characteristics and the manufacturing cost required for the grain-oriented electrical steel sheet to be finally manufactured.
- ⁇ Hot plate pickling process> when performing hot-rolled steel sheet after the hot-rolling step, or when hot-rolled sheet annealing, for the hot-rolled annealed sheet after the hot-rolled sheet annealing step, if necessary, on the surface Pickling is performed to remove the generated scale.
- the pickling conditions are not particularly limited and may be known conditions.
- the hot-rolled steel sheet or hot-rolled annealed sheet after the hot-rolling step, the hot-rolled sheet annealing step, or the hot-rolled sheet pickling step is cold-rolled once or twice or more with an intermediate annealing. Roll to give a cold rolled steel sheet.
- the steel sheet after the cold rolling process is referred to as a cold rolled steel sheet.
- a preferable cold rolling rate (cumulative cold rolling rate without intermediate annealing, or cumulative cold rolling rate after performing intermediate annealing) in the final cold rolling is preferably 80% or more, and more preferably. 90% or more.
- the preferable upper limit of the final cold rolling rate is 95%.
- Final cold rolling rate (%) (1-sheet thickness of steel sheet after final cold rolling/sheet thickness of steel sheet before final cold rolling) x 100
- ⁇ Decarburization annealing process> the cold-rolled steel sheet produced in the cold rolling step is subjected to magnetic domain control treatment, if necessary, and then decarburization annealed to perform primary recrystallization. Further, in the decarburization annealing, C that adversely affects the magnetic properties is removed from the steel sheet.
- the steel sheet after the decarburizing and annealing step is called a decarburizing and annealing sheet.
- the annealing is performed at an annealing temperature of 750 to 900° C. for 10 to 600 seconds in an atmosphere having an oxidation degree of PH 2 O/PH 2 of 0.18 to 0.80. ..
- the degree of oxidation PH 2 O/PH 2 can be defined by the ratio of the partial pressure of water vapor PH 2 O (atm) and the partial pressure of hydrogen PH 2 (atm) in the atmosphere.
- the holding time is less than 10 seconds, decarburization cannot be sufficiently performed. On the other hand, if it exceeds 600 seconds, the primary recrystallized grain size exceeds the desired size, and the magnetism after finish annealing deteriorates.
- the heating rate in the temperature elevation process up annealing temperature may be controlled.
- the average heating rate may be 5 to 1000° C./sec.
- the average heating rate may be 5 to 3000° C./sec.
- the decarburization annealing step further, before or during the above holding, at any one of the following steps, or at two or more stages, annealing is performed in an atmosphere containing ammonia to nitride the cold rolled steel sheet, Nitriding may be performed.
- the decarburization annealing step preferably includes a nitriding treatment.
- inhibitors such as AlN and (Al,Si)N are generated before the secondary recrystallization in the finish annealing step, so that the secondary recrystallization can be stably performed. Can be expressed. ⁇
- the conditions of the nitriding treatment are not particularly limited, but it is preferable to perform the nitriding treatment so that the nitrogen content is increased by 0.003% or more, preferably 0.005% or more, more preferably 0.007% or more. Since the effect is saturated when the nitrogen (N) content is 0.030% or more, the nitriding treatment may be performed so as to be 0.030% or less.
- the conditions of the nitriding treatment are not particularly limited, and known conditions may be used.
- the nitriding treatment is performed after maintaining the oxidation degree (PH 2 O/PH 2 ) at 0.01 to 0.15 and 750° C. to 900° C. for 10 to 600 seconds, the cold rolled steel sheet is cooled to room temperature. Without performing, the nitriding treatment is performed by holding in an atmosphere containing ammonia in the process of cooling. It is preferable to set the degree of oxidation (PH 2 O/PH 2 ) in the range of 0.0001 to 0.01 in the process of lowering the temperature.
- ammonia gas is added to the atmosphere gas having this oxidation degree. Just install it.
- the decarburization annealed sheet after the decarburization annealing step (including the decarburized annealed sheet subjected to the nitriding treatment) is subjected to magnetic domain control treatment, if necessary, and then treated with Al 2 O 3 .
- An annealing separating agent containing MgO is applied, and the applied annealing separating agent is dried.
- the annealing separator contains MgO and does not contain Al 2 O 3 , a forsterite coating is formed on the steel sheet in the finish annealing step.
- the annealing separator contains Al 2 O 3 but does not contain MgO, mullite (3Al 2 O 3 ⁇ 2SiO 2 ) is formed on the steel sheet. Since this mullite interferes with the movement of the domain wall, it causes deterioration of the magnetic properties of the grain-oriented electrical steel sheet.
- an annealing separator containing Al 2 O 3 and MgO is used as the annealing separator.
- MgO/(MgO+Al 2 O 3 ) which is a mass ratio of MgO and Al 2 O 3 , is 5 to 50%, and hydrated water is 1.5 mass% or less.
- MgO/(MgO+Al 2 O 3 ) is less than 5%, a large amount of mullite is formed, so that iron loss is deteriorated.
- forsterite is formed, so that the iron loss is deteriorated.
- the hydrated water content in the annealing separator is more than 1.5% by mass, the secondary recrystallization becomes unstable, or the steel sheet surface is oxidized (SiO 2 is formed) during the finish annealing, and the steel sheet surface May be difficult to smooth.
- the lower limit of the hydrated water content is not particularly limited, but may be 0.1% by mass, for example.
- the annealing separator is applied to the steel plate surface by water slurry coating or electrostatic coating.
- manganese nitride, iron nitride, chromium nitride, etc. are added to the annealing separating agent such as nitride that decomposes and denitrifies the decarburized steel sheet or decarbonitrided sheet before secondary recrystallization in the final annealing step. You may.
- ⁇ Finishing annealing process> The decarburized annealed plate coated with the annealing separator is subjected to finish annealing to obtain a finish annealed plate.
- finish annealing plate By subjecting the decarburized annealed plate coated with the annealing separator to finish annealing, secondary recrystallization proceeds and the crystal orientation is accumulated in the ⁇ 110 ⁇ 001> orientation.
- the steel sheet after the finish annealing process is called a finish annealing plate.
- the decarburized annealed plate coated with the annealing separator is held at a temperature of 1100 to 1200° C. for 10 hours or more in a mixed gas atmosphere containing 50% or more by volume of hydrogen. ..
- the upper limit of the annealing time is not particularly limited, but may be 30 hours, for example.
- annealing separating agent removal process In the annealing separating agent removing step, excess annealing separating agent such as unreacted annealing separating agent which has not reacted with the steel sheet in finish annealing is removed by washing from the surface of the steel sheet after finish annealing (finish annealing sheet).
- an aqueous solution containing at least one of triethanolamine, rosinamine, or mecaptan added as an inhibitor (corrosion inhibitor) is used for washing and removal. It is important to control the total amount of iron-based hydroxides and iron-based oxides on the surface of the steel plate to 0.9 g/m 2 or less per one side by this cleaning treatment.
- Excessive annealing separator removal on the surface of the steel sheet is insufficient, and when the total amount of iron-based hydroxide and iron-based oxide on the surface of the steel sheet exceeds 0.9 g/m 2 per side, the exposed surface of the base steel Since it becomes insufficient, the surface of the steel sheet may not be sufficiently mirror-finished.
- the lower limits of the amount of iron-based hydroxide and the amount of iron-based oxide are not particularly limited, but may be 0.01 g/m 2 , for example.
- a scrubber may be used for removal.
- the scrubber it is possible to reliably remove the excess annealing separator that deteriorates the wettability in the insulating film forming step.
- pickling may be performed using an acidic solution having a volume ratio concentration of less than 20%.
- the acid one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, chloric acid, an aqueous solution of chromium oxide, chromium sulfuric acid, permanganic acid, peroxosulfuric acid and peroxophosphoric acid are contained in a total amount of less than 20% by volume. It is preferable to use a mixed solution, more preferably less than 10% by volume.
- the lower limit of the volume specific concentration is not particularly limited, but may be 0.1% by volume, for example. By using such a solution, the excess annealing separator on the surface of the steel sheet can be efficiently removed.
- the volume% may be a ratio based on the volume at room temperature.
- the solution temperature is preferably 20-80°C.
- a finish annealed plate having a smoothed surface is obtained by adjusting the average roughness Ra to 0.10 ⁇ m or less by chemical polishing. ..
- the lower limit of the average roughness Ra is not particularly limited, but may be 0.01 ⁇ m, for example.
- Electrolytic polishing is one of the known methods for chemical polishing to obtain a smooth surface.
- a method of electrolytic polishing for example, the surface of the steel sheet can be smoothed by electrically polishing in an electrolytic solution of phosphoric acid and chromic anhydride.
- an electrolytic solution of phosphoric acid and chromic anhydride There is also a method of using a liquid obtained by adding a small amount of hydrofluoric acid to hydrogen peroxide water.
- the irregularities increase the iron loss due to the movement of the domain wall being hindered.
- a smooth state with extremely high flatness is obtained, and the movement of the domain wall is smoothly performed, resulting in a high iron loss improving effect. Can be obtained.
- ⁇ Insulating film forming step> an insulating film is formed on the surface of the smoothed finish annealed plate after performing magnetic domain control treatment as needed.
- the steel sheet after the insulating film forming step is called a grain-oriented electrical steel sheet.
- This insulating coating reduces the iron loss as a single steel plate by applying tension to the grain-oriented electrical steel sheets, and also improves the electrical insulation between the steel sheets when the grain-oriented electrical steel sheets are laminated and used. By securing it, the iron loss as an iron core is reduced.
- the insulating coating is formed by applying a coating forming solution (coating forming solution 1) containing phosphate, colloidal silica and crystalline phosphide on the surface of the finish annealed plate, baking it at 350 to 1150° C., and lowering the temperature of phosphoric acid. It is formed by coating a film-forming solution containing a salt and colloidal silica but not a crystalline phosphide (film-forming solution 2) and baking at 350 to 1150°C.
- coating forming solution 1 containing phosphate, colloidal silica and crystalline phosphide
- crystalline phosphide a compound whose chemical composition is such that the total content of Fe, Cr, P, and O is 70 atomic% or more and 100 atomic% or less and Si is limited to 10 atomic% or less may be used. ..
- the rest of the chemical composition of this compound may be impurities.
- crystalline phosphide includes Fe 3 P, Fe 2 P, FeP, FeP 2 , Fe 2 P 2 O 7 , (Fe, Cr) 3 P, (Fe, Cr) 2 P, (Fe, Cr)P. , (Fe,Cr)P 2 , and (Fe,Cr) 2 P 2 O 7 are preferably one kind or two or more kinds.
- the average diameter of the crystalline phosphide is preferably 10 to 300 nm.
- the crystalline phosphide in the film forming solution 1 is preferably 3 to 35% by mass ratio.
- the film forming solution 1 may be the same solution as the film forming solution 2 except that the above crystalline phosphide is controlled.
- the film forming solution 1 may contain phosphate or colloidal silica as a main component.
- the baking temperature of the film forming solution 1 may be 350 to 1150°C. Further, the baking time is preferably 5 to 300 seconds, and a mixed gas of steam, nitrogen and hydrogen having an atmosphere oxidation degree PH 2 O/PH 2 of 0.001 to 1.0 is preferable. By this heat treatment, an insulating film having a crystalline phosphide-containing layer can be formed. In order to exhibit the adhesion of the insulating coating with good reproducibility, the degree of oxidation PH 2 O/PH 2 is 0.01 to 0.15, the baking temperature is 650 to 950° C., and the holding time is 30 to 270 seconds. More preferable.
- the steel sheet is cooled while keeping the degree of oxidation of the atmosphere low so that the crystalline phosphide does not chemically change (the crystalline phosphide does not deteriorate by taking in water during cooling).
- the cooling atmosphere is preferably an atmosphere having an oxidation degree PH 2 O/PH 2 of 0.01 or less.
- the film-forming solution 1 is baked, and after the temperature is lowered to, for example, room temperature (about 25° C.), the film-forming solution 2 mainly containing phosphate and colloidal silica and containing no crystalline phosphide is applied and further baked.
- the film forming solution 2 may be baked at a baking temperature of 350 to 1150°C. Further, the baking time is preferably 5 to 300 seconds, and a mixed gas of steam, nitrogen and hydrogen having an atmosphere oxidation degree PH 2 O/PH 2 of 0.001 to 1.0 is preferable.
- the insulating coating having no crystalline phosphide-containing layer can be formed on the insulating coating having the crystalline phosphide-containing layer.
- the degree of oxidation PH 2 O/PH 2 is 0.01 to 0.15
- the baking temperature is 650 to 950° C.
- the holding time is 30 to 270 seconds. More preferable.
- the steel sheet is cooled while keeping the degree of oxidation of the atmosphere low so that the crystalline phosphide does not chemically change (the crystalline phosphide does not deteriorate by taking in water during cooling).
- the cooling atmosphere is preferably an atmosphere having an oxidation degree PH 2 O/PH 2 of 0.01 or less.
- the crystalline phosphide-containing layer and the insulating film containing no crystalline phosphide that is in contact with the crystalline phosphide-containing layer can be formed.
- the film forming solution 1 and the film forming solution 2 can be applied to the surface of the steel sheet by a wet application method such as a roll coater.
- ⁇ Magnetic domain control process> In the method for manufacturing a grain-oriented electrical steel sheet according to the present embodiment, smoothing is performed between the cold rolling step and the decarburizing annealing step (first), between the decarburizing annealing step and the annealing separator application step (second).
- a magnetic domain control step of performing a magnetic domain control process may be provided either between the step and the insulating film forming step (third) or after the insulating film forming step (fourth).
- the rolling direction The width of the 180° magnetic domain may be narrowed (the 180° magnetic domain is subdivided) by forming linear or dot-shaped groove portions extending in the direction intersecting with each other at predetermined intervals along the rolling direction.
- the magnetic domain control treatment when the magnetic domain control treatment is performed after the insulating film forming step, by forming linear or dotted stress-strained portions or grooves extending in the direction intersecting the rolling direction at predetermined intervals along the rolling direction.
- the width of the 180° magnetic domain may be narrowed (the 180° magnetic domain may be subdivided).
- Laser beam irradiation, electron beam irradiation, etc. can be applied when forming the stress-strained portion. Further, in the case of forming the groove portion, a mechanical groove forming method using a gear or the like, a chemical groove forming method of forming a groove by electrolytic etching, a thermal groove forming method by laser irradiation, and the like can be applied. If damage to the insulation coating due to the formation of stress-strained portions or grooves and deterioration of characteristics such as insulation properties, the insulation coating may be formed again to repair the damage.
- FIG. 1 shows an example of a method for manufacturing a grain-oriented electrical steel sheet according to this embodiment.
- a process surrounded by a solid line indicates an essential process, and a process surrounded by a broken line indicates an arbitrary process.
- the grain-oriented electrical steel sheet manufactured by the manufacturing method according to this embodiment does not have a forsterite coating.
- this grain-oriented electrical steel sheet has a mother steel sheet, an intermediate layer disposed in contact with the mother steel sheet, and an insulating coating disposed in contact with the intermediate layer and serving as the outermost surface.
- X-ray diffraction may be performed on the surface of the grain-oriented electrical steel sheet from which the insulating coating has been removed, and the obtained X-ray diffraction spectrum may be collated with a PDF (Powder Diffraction File).
- JCPDS number: 34-189 may be used to identify forsterite (Mg 2 SiO 4 ).
- the main component of the X-ray diffraction spectrum is not forsterite, it is determined that the grain-oriented electrical steel sheet does not have a forsterite coating.
- the grain-oriented electrical steel sheet having the coating may be dipped in a high temperature alkaline solution. Specifically, by dipping in a sodium hydroxide aqueous solution of NaOH: 30% by mass+H 2 O: 70% by mass for 20 minutes at 80° C., washing with water and drying, an insulating coating is formed from the grain-oriented electrical steel sheet. Can be removed.
- the alkaline solution dissolves only the insulating coating
- the acidic solution such as hydrochloric acid dissolves the forsterite coating.
- the grain-oriented electrical steel sheet produced by the production method according to the present embodiment does not have a forsterite coating, it has excellent magnetic characteristics (iron loss characteristics), and since each manufacturing step is optimally controlled, coating adhesion is improved. Is also excellent.
- the condition in the example is one condition example adopted for confirming the feasibility and effect of the present invention, and the present invention is based on this one condition example. It is not limited.
- the present invention can employ various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
- the average heating rate during the heating process up to the annealing temperature was less than 15°C/sec.
- an annealing separator having a ratio of Al 2 O 3 to MgO (MgO/(Al 2 O 3 +MgO)) and hydrated water content shown in Tables 2 to 4 was applied and dried.
- the decarburized annealed plate coated with the annealing separator was subjected to finish annealing at 1100°C or 1200°C.
- the finish annealing conditions were as shown in Tables 5-7.
- the excess annealing separating agent is removed from the surface of the finish annealed plate by washing with a solution containing an inhibitor which is at least one of triethanolamine, rosinamine, or mecaptan. did.
- pickling was performed if necessary.
- the pickling was performed by immersing the excess annealing separator in the aqueous sulfuric acid solution (volume ratio concentration of sulfuric acid: 1% by volume).
- the surface of the finish-annealed plate was subjected to chemical polishing (electrolytic polishing) in an electrolytic solution of phosphoric acid and chromic anhydride to obtain the average roughness Ra shown in Tables 8 to 10.
- a film-forming solution (film-forming solution 1) was prepared by stirring and mixing 10 parts by mass of fine powder of crystalline phosphide with 100 parts by mass of an aqueous solution containing magnesium phosphate and colloidal silica, and optionally chromic anhydride.
- a film-forming solution (film-forming solution 2) containing no crystalline phosphide, containing colloidal silica and phosphate as the main components, and containing chromic anhydride as needed, was applied, and the results are shown in Tables 8-10. It was baked at the temperature shown in. These were baked to form an insulating film.
- the crystalline phosphide mixed in the film-forming solution 1 was Fe 3 P, Fe 2 P, FeP, FeP 2 , Fe 2 P 2 O 7 , (Fe, Cr) 3 P, (Fe, Cr) 2 P. , (Fe,Cr)P, (Fe,Cr)P 2 , and (Fe,Cr) 2 P 2 O 7 .
- ⁇ Film adhesion> The test piece taken from the produced grain-oriented electrical steel sheet was wound (180° bent) around a cylinder having a diameter of 20 mm, and the film adhesion of the insulating film was evaluated by the film remaining area ratio when the film was bent back. In the evaluation of the coating adhesion of the insulating coating, the presence or absence of peeling of the insulating coating was visually determined. Without peeling from the steel sheet, the residual film area ratio is 90% or more (VERY GOOD), 85% or more and less than 90% is ⁇ (GOOD), 80% or more and less than 85% is ⁇ (POOR), and less than 80% is ⁇ . (NG). The case where the coating film residual area ratio was 85% or more ( ⁇ or ⁇ above) was judged to be acceptable. The results are shown in Tables 11 to 13.
- the present invention it is possible to provide a method for producing a grain-oriented electrical steel sheet having no forsterite coating and having excellent magnetic properties and coating adhesion. Since the obtained grain-oriented electrical steel sheet is excellent in magnetic properties and coating adhesion, the present invention has high industrial applicability.
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Abstract
Description
本願は、2019年1月16日に、日本に出願された特願2019-005085号に基づき優先権を主張し、その内容をここに援用する。
(1)本発明の一態様に係る方向性電磁鋼板の製造方法は、
化学組成として、質量%で、
C:0.030~0.100%、
Si:0.80~7.00%、
Mn:0.01~1.00%、
S及びSeの合計:0~0.060%、
酸可溶性Al:0.010~0.065%、
N:0.004~0.012%、
Cr:0~0.30%、
Cu:0~0.40%、
P:0~0.50%、
Sn:0~0.30%、
Sb:0~0.30%、
Ni:0~1.00%、
B:0~0.008%、
V:0~0.15%、
Nb:0~0.20%、
Mo:0~0.10%、
Ti:0~0.015%、
Bi:0~0.010%、を含有し、
残部がFeおよび不純物からなる鋼片を、熱間圧延して熱延鋼板を得る熱延工程と、
前記熱延鋼板に冷間圧延を施して冷延鋼板を得る冷延工程と、
前記冷延鋼板に脱炭焼鈍を行って脱炭焼鈍板を得る脱炭焼鈍工程と、
前記脱炭焼鈍板に、Al2O3とMgOとを含有する焼鈍分離剤を塗布して乾燥させる焼鈍分離剤塗布工程と、
前記焼鈍分離剤が塗布された前記脱炭焼鈍板に仕上げ焼鈍を行い、仕上げ焼鈍板を得る仕上げ焼鈍工程と、
前記仕上げ焼鈍板の表面から余剰の焼鈍分離剤を除去する焼鈍分離剤除去工程と、
前記余剰の焼鈍分離剤が除去された前記仕上げ焼鈍板の表面を平滑化する平滑化工程と、
平滑化された前記仕上げ焼鈍板の表面に絶縁被膜を形成する絶縁被膜形成工程と、
を備え、
前記脱炭焼鈍工程では、
酸化度であるPH2O/PH2が0.18~0.80である雰囲気下で、焼鈍温度750~900℃で、10~600秒保持を行い、
前記焼鈍分離剤塗布工程では、
前記焼鈍分離剤における、前記MgOと前記Al2O3との質量比率であるMgO/(MgO+Al2O3)を5~50%、水和水分を1.5質量%以下とし、
前記仕上げ焼鈍工程では、
前記焼鈍分離剤が塗布された前記脱炭焼鈍板を、体積率で水素を50%以上含む混合ガス雰囲気中で、1100~1200℃の温度で10時間以上保持し、
前記焼鈍分離剤除去工程では、
前記仕上げ焼鈍板の表面から余剰の焼鈍分離剤を、トリエタノールアミン、ロジンアミン、またはメカプタンの少なくとも1つであるインヒビターを添加した溶液を用いて水洗して除去し、鋼板表面における鉄系水酸化物量及び鉄系酸化物量を片面当り0.9g/m2以下にし、
前記平滑化工程では、
化学研磨により、前記余剰の焼鈍分離剤が除去された前記仕上げ焼鈍板の表面を、平均粗さRaが0.1μm以下となるようにし、
前記絶縁被膜形成工程では、
リン酸塩、コロイダルシリカ、および結晶性燐化物を含む被膜形成溶液を塗布して350~1150℃で焼き付け、降温後に、リン酸塩およびコロイダルシリカを含むが結晶性燐化物を含まない被膜形成溶液を塗布して350~1150℃で焼き付けて絶縁被膜を形成する。
(2)上記(1)に記載の方向性電磁鋼板の製造方法では、前記熱延工程と前記冷延工程との間に、前記熱延鋼板を焼鈍する熱延板焼鈍工程、または酸洗を行う熱延板酸洗工程の少なくとも1つを備えてもよい。
(3)上記(1)又は(2)に記載の方向性電磁鋼板の製造方法では、前記脱炭焼鈍工程で、前記冷延鋼板を、アンモニアを含有する雰囲気中で焼鈍する窒化処理を行ってもよい。
(4)上記(1)~(3)のいずれか1つに記載の方向性電磁鋼板の製造方法では、前記冷延工程と前記脱炭焼鈍工程との間、前記脱炭焼鈍工程と前記焼鈍分離剤塗布工程との間、前記平滑化工程と前記絶縁被膜形成工程との間、または前記絶縁被膜形成工程後のいずれかに、磁区制御処理を行う磁区制御工程を備えてもよい。
(5)上記(1)~(4)のいずれか1つに記載の方向性電磁鋼板の製造方法では、前記焼鈍分離剤除去工程で、前記水洗後に、体積比濃度が20%未満の酸性溶液を用いて酸洗を行ってもよい。
(6)上記(1)~(5)のいずれか1つに記載の方向性電磁鋼板の製造方法では、前記鋼片が、化学組成として、質量%で、
Cr:0.02~0.30%、
Cu:0.05~0.40%、
P:0.005~0.50%、
Sn:0.02~0.30%、
Sb:0.01~0.30%、
Ni:0.01~1.00%、
B:0.0005~0.008%、
V:0.002~0.15%、
Nb:0.005~0.20%、
Mo:0.005~0.10%、
Ti:0.002~0.015%、及び
Bi:0.001~0.010%、
からなる群から選択される少なくとも1種を含有してもよい。
(i)所定の化学組成を有する鋼片を、熱間圧延して熱延鋼板を得る熱延工程
(ii)前記熱延鋼板を、1回または中間焼鈍を挟む2回以上の冷間圧延を施して冷延鋼板を得る冷延工程
(iii)前記冷延鋼板に脱炭焼鈍を行って脱炭焼鈍板を得る脱炭焼鈍工程
(iv)前記脱炭焼鈍板に、Al2O3とMgOとを含有する焼鈍分離剤を塗布して乾燥させる焼鈍分離剤塗布工程
(v)焼鈍分離剤が塗布された前記脱炭焼鈍板に仕上げ焼鈍を行い、仕上げ焼鈍板を得る仕上げ焼鈍工程
(vi)前記仕上げ焼鈍板の表面から余剰の焼鈍分離剤を除去する焼鈍分離剤除去工程
(vii)前記余剰の焼鈍分離剤が除去された前記仕上げ焼鈍板の表面を平滑化する平滑化工程
(viii)平滑化された前記仕上げ焼鈍板の表面に絶縁被膜を形成する絶縁被膜形成工程
(I)熱延鋼板を焼鈍する熱延板焼鈍工程
(II)熱延鋼板を酸洗する熱延板酸洗工程
(III)磁区制御処理を行う磁区制御工程
熱延工程では、化学組成として、質量%で、C:0.030~0.100%、Si:0.80~7.00%、Mn:0.01~1.00%、S+Seの合計:0~0.060%、酸可溶性Al:0.010~0.065%、N:0.004~0.012%、Cr:0~0.30%、Cu:0~0.40%、P:0~0.50%、Sn:0~0.30%、Sb:0~0.30%、Ni:0~1.00%、B:0~0.008%、V:0~0.15%、Nb:0~0.20%、Mo:0~0.10%、Ti:0~0.015%、Bi:0~0.010%、を含有し、残部がFeおよび不純物からなる鋼片を、熱間圧延して熱延鋼板を得る。本実施形態では、熱延工程後の鋼板を、熱延鋼板と呼ぶ。
C(炭素)は、一次再結晶組織の制御に有効な元素であるが、磁気特性に悪影響を及ぼすので、仕上げ焼鈍前に脱炭焼鈍で除去する元素である。鋼片のC含有量が0.100%を超えると、脱炭焼鈍時間が長くなり、生産性が低下する。そのため、C含有量は0.100%以下とする。好ましくは0.085%以下、より好ましくは0.070%以下である。
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0.80%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。したがって、Si含有量は0.80%以上である。Si含有量は好ましくは2.00%以上であり、より好ましくは2.50%以上である。
一方、Si含有量が7.00%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。したがって、Si含有量は7.00%以下である。Si含有量は好ましくは4.50%以下であり、さらに好ましくは4.00%以下である。
マンガン(Mn)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。また、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含有量が0.01~1.00%の範囲内にある場合に、二次再結晶が安定する。したがって、Mn含有量は、0.01~1.00%である。Mn含有量の好ましい下限は0.08%であり、さらに好ましくは0.09%である。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。
S(硫黄)及びSe(セレン)は、Mnと結合して、インヒビターとして機能するMnS及び/又はMnSeを形成する元素である。
S及びSeのいずれかまたは両方の合計(S+Se)が0.060%超であると、熱間圧延後にMnSやMnSeの析出分散が不均一となる。この場合、所望の二次再結晶組織が得られず、磁束密度が低下したり、純化後にMnSが鋼中に残存し、ヒステリシス損が劣化したりする。そのため、SとSeとの合計含有量は、0.060%以下とする。
SとSeとの合計含有量の下限は、特に制限されず、0%であればよい。この下限は、0.003%以上としてもよい。インヒビターとして用いる場合、好ましくは0.015%以上である。
酸可溶性Al(アルミニウム)(Sol.Al)は、Nと結合して、インヒビターとして機能するAlNや(Al、Si)Nを生成する元素である。酸可溶性Alが0.010%未満では、効果が十分に発現せず、二次再結晶が十分に進行しない。そのため、酸可溶性Al含有量は0.010%以上とする。酸可溶性Al含有量は好ましくは0.015%以上、より好ましくは0.020%以上である。
N(窒素)は、Alと結合して、インヒビターとして機能するAlNや(Al、Si)Nを形成する元素である。N含有量が0.004%未満では、AlNや(Al、Si)Nの形成が不十分となるので、Nは0.004%以上とする。好ましくは0.006%以上、より好ましくは0.007%以上である。
一方、N含有量が0.012%超であると、鋼板中にブリスター(空孔)が形成されることが懸念される。そのため、N含有量を0.012%以下とする。
Cr(クロム)は、Siと同様に、電気抵抗を高めて鉄損を低減するのに有効な元素である。従って、Crを含有させてもよい。上記効果を得る場合、Cr含有量は、0.02%以上であることが好ましく、0.05%以上であることがより好ましい。
一方で、Cr含有量が0.30%を超えると、磁束密度の低下が問題となるので、Cr含有量の上限は、0.30%であることが好ましく、0.20%であることがより好ましく、0.12%であることがさらに好ましい。
Cu(銅)も、電気抵抗を高めて鉄損を低減するのに有効な元素である。従って、Cuを含有させてもよい。この効果を得る場合、Cu含有量は、0.05%以上であることが好ましく、0.10%以上であることがより好ましい。
一方、Cu含有量が0.40%を超えると、鉄損低減効果が飽和してしまうとともに、熱間圧延時に“カッパーヘゲ”なる表面疵の原因になることがある。そのため、Cu含有量の上限は、0.40%であることが好ましく、0.30%であることがより好ましく、0.20%であることがさらに好ましい。
P(リン)も、電気抵抗を高めて鉄損を低減するのに有効な元素である。従って、Pを含有させてもよい。この効果を得る場合、P含有量は、0.005%以上であることが好ましく、0.010%以上であることがより好ましい。
一方、P含有量が0.50%を超えると、圧延性に問題が生じることがある。そのため、P含有量の上限は、0.50%であることが好ましく、0.20%であることがより好ましく、0.15%であることがさらに好ましい。
[Sb:0~0.30%]
Sn(スズ)およびSb(アンチモン)は、二次再結晶を安定化させ、{110}<001>方位を発達させるのに有効な元素である。従って、SnまたはSbを含有させてもよい。この効果を得る場合、Sn含有量は、0.02%以上であることが好ましく、0.05%以上であることがより好ましい。また、Sb含有量は、0.01%以上であることが好ましく、0.03%以上であることがより好ましい。
一方、Snが0.30%超、またはSbが0.30%超となると、磁気特性に悪影響を及ぼすおそれがある。そのため、Sn含有量、Sb含有量の上限をそれぞれ0.30%とすることが好ましい。Sn含有量の上限は、0.15%であることがより好ましく、0.10%であることがさらに好ましい。Sb含有量の上限は、0.15%であることがより好ましく、0.10%であることがさらに好ましい。
Ni(ニッケル)も、電気抵抗を高めて鉄損を低減するのに有効な元素である。また、Niは、熱延鋼板の金属組織を制御して、磁気特性を高めるうえで有効な元素である。従って、Niを含有させてもよい。上記効果を得る場合、Ni含有量は、0.01%以上であることが好ましく、0.02%以上であることがより好ましい。
一方、Ni含有量が1.00%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、Ni含有量を1.00%以下とすることが好ましく、0.20%以下とすることがより好ましく、0.10%以下とすることがさらに好ましい。
B(ボロン)は、Nと結合してインヒビター効果を発揮するBNを形成するのに有効な元素である。従って、Bを含有させてもよい。上記効果を得る場合、B含有量は、0.0005%以上であることが好ましく、0.0010%以上であることがより好ましい。
一方、B含有量が0.008%を超えると、磁気特性に悪影響を及ぼすおそれがある。そのため、B含有量の上限は、0.008%であることが好ましく、0.005%であることがより好ましく、0.003%であることがさらに好ましい。
[Nb:0~0.20%]
[Ti:0~0.015%]
V(バナジウム)、Nb(ニオブ)、及びTi(チタン)は、NやCと結合してインヒビターとして機能する元素である。従って、V、Nb、またはTiを含有させてもよい。上記効果を得る場合、V含有量は、0.002%以上であることが好ましく、0.010%以上であることがより好ましい。Nb含有量は、0.005%以上であることが好ましく、0.020%以上であることがより好ましい。Ti含有量は、0.002%以上であることが好ましく、0.004%以上であることがより好ましい。
一方、鋼片がVを0.15%超、Nbを0.20%超、Tiを0.015%超の範囲で含有すると、これらの元素が最終製品に残留して、最終製品として、V含有量が0.15%を超え、Nb含有量が0.20%を超え、またはTi含有量が0.015%を超える場合がある。この場合、最終製品(電磁鋼板)の磁気特性が劣化するおそれがある。
そのため、V含有量の上限は、0.15%であることが好ましく、0.10%であることがより好ましく、0.05%であることがさらに好ましい。Ti含有量の上限は、0.015%であることが好ましく、0.010%であることがより好ましく、0.008%であることがさらに好ましい。Nb含有量の上限は、0.20%であることが好ましく、0.10%であることがより好ましく、0.08%であることがさらに好ましい。
Mo(モリブデン)も、電気抵抗を高めて鉄損を低減するのに有効な元素である。従って、Moを含有させてもよい。上記効果を得る場合、Mo含有量は、0.005%以上であることが好ましく、0.01%以上であることがより好ましい。
一方、Mo含有量が0.10%を超えると、鋼板の圧延性に問題が生じることがある。そのため、Mo含有量の上限は、0.10%であることが好ましく、0.08%であることがより好ましく、0.05%であることがさらに好ましい。
Bi(ビスマス)は、硫化物等の析出物を安定化してインヒビターとしての機能を強化するのに有効な元素である。従って、Biを含有させてもよい。上記効果を得る場合、Bi含有量は、0.001%以上であることが好ましく、0.002%以上であることがより好ましい。
一方、Bi含有量が0.010%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、Bi含有量の上限は、0.010%であることが好ましく、0.008%であることがより好ましく、0.006%であることがさらに好ましい。
熱間圧延条件については特に限定されない。例えば、以下の条件である。
熱間圧延に先立ちスラブを加熱する。スラブを周知の加熱炉又は周知の均熱炉に装入して、加熱する。1つの方法として、スラブを1280℃以下に加熱する。スラブの加熱温度を1280℃以下とすることにより、たとえば、1280℃よりも高い温度で加熱した場合の諸問題(専用の加熱炉が必要なこと、及び溶融スケール量の多さ等)を回避することができる。スラブの加熱温度の下限値は特に限定されない。加熱温度が低すぎる場合、熱間圧延が困難になって、生産性が低下することがある。したがって、加熱温度は、1280℃以下の範囲で生産性を考慮して設定すればよい。スラブの加熱温度の好ましい下限は1100℃である。スラブの加熱温度の好ましい上限は1250℃である。
スラブ加熱工程そのものを省略して、鋳造後、スラブの温度が下がるまでに熱間圧延を開始することも可能である。
熱延工程における仕上げ温度(仕上げ圧延機にて最後に鋼板を圧下する仕上げ圧延スタンドの出側での鋼板温度)は、たとえば700~1150℃である。以上の熱延工程により、熱延鋼板を製造する。
熱延板焼鈍工程では、必要に応じて、熱延工程によって得られた熱延鋼板に対して、焼鈍(熱延板焼鈍)を行って熱延焼鈍板を得る。本実施形態では、熱延板焼鈍工程後の鋼板を、熱延焼鈍板と呼ぶ。
熱延板焼鈍は必ずしも行う必要がなく、熱延板焼鈍工程の実施の有無は、最終的に製造される方向性電磁鋼板に要求される特性及び製造コストに応じて決定すればよい。
熱延板酸洗工程では、熱延工程後の熱延鋼板、または熱延板焼鈍を行った場合には、熱延板焼鈍工程後の熱延焼鈍板に対し、必要に応じて、表面に生成したスケールを除去するため、酸洗を行う。酸洗条件については特に限定されず、公知の条件で行えばよい。
冷延工程では、熱延工程後、熱延板焼鈍工程後、または熱延板酸洗工程後の熱延鋼板または熱延焼鈍板に対し、1回または中間焼鈍を挟む2回以上の冷間圧延を施して冷延鋼板とする。本実施形態では、冷延工程後の鋼板を、冷延鋼板と呼ぶ。
最終の冷間圧延率(%)=(1-最終の冷間圧延後の鋼板の板厚/最終の冷間圧延前の鋼板の板厚)×100
脱炭焼鈍工程では、冷延工程により製造された冷延鋼板に対して、必要に応じて磁区制御処理を行った後、脱炭焼鈍を実施して一次再結晶させる。また、脱炭焼鈍では、磁気特性に悪影響を及ぼすCを鋼板から除去する。本実施形態では、脱炭焼鈍工程後の鋼板を、脱炭焼鈍板と呼ぶ。
また、焼鈍温度が750℃未満であると、脱炭不良が生じ、仕上げ焼鈍後の磁性が劣化する。一方、900℃超であると一次再結晶粒径が所望のサイズを超えてしまうため、仕上げ焼鈍後の磁性が劣化する。
また、保持時間が10秒未満であると、脱炭を充分に行うことができない。一方、600秒超であると、一次再結晶粒径が所望のサイズを超えてしまうため、仕上げ焼鈍後の磁性が劣化する。
例えば、窒化処理を、酸化度(PH2O/PH2)を0.01~0.15、750℃~900℃で10~600秒保持した後に行う場合には、冷延鋼板を室温まで冷却することなく、降温の過程でアンモニアを含有する雰囲気中で保持して窒化処理を行う。降温の過程で酸化度(PH2O/PH2)を0.0001~0.01の範囲とすることが好ましい。窒化処理を、酸化度(PH2O/PH2)を0.01~0.15、750~900℃で10~600秒の保持中に行う場合には、この酸化度の雰囲気ガスにアンモニアを導入すればよい。
焼鈍分離剤塗布工程では、脱炭焼鈍工程後の脱炭焼鈍板(窒化処理を行った脱炭焼鈍板も含む)に対し、必要に応じて磁区制御処理を行った後、Al2O3とMgOとを含有する焼鈍分離剤を塗布し、塗布した焼鈍分離剤を乾燥させる。
MgO/(MgO+Al2O3)が5%未満では、多量のムライトが形成されるため、鉄損が劣化する。一方、50%超では、フォルステライトが形成されるため、鉄損が劣化する。
また、焼鈍分離剤における水和水分が1.5質量%超であると、二次再結晶が不安定になったり、仕上げ焼鈍中に鋼板表面が酸化され(SiO2が形成され)、鋼板表面の平滑化が困難となる場合がある。水和水分の下限は、特に制限されないが、例えば0.1質量%とすればよい。
上記焼鈍分離剤が塗布された脱炭焼鈍板に仕上げ焼鈍を行い、仕上げ焼鈍板とする。焼鈍分離剤を塗布した脱炭焼鈍板に仕上げ焼鈍を施すことで、二次再結晶が進行し、結晶方位が{110}<001>方位に集積する。本実施形態では、仕上げ焼鈍工程後の鋼板を、仕上げ焼鈍板と呼ぶ。
焼鈍分離剤除去工程では、仕上げ焼鈍後の鋼板(仕上げ焼鈍板)の表面から、仕上げ焼鈍で鋼板と反応しなかった未反応の焼鈍分離剤等の余剰な焼鈍分離剤を水洗除去する。
上記のような水洗を行うことで地鉄を露出させた後に、化学研磨により平均粗さRaを0.10μm以下に調整することで表面(地鉄面)が平滑化された仕上げ焼鈍板を得る。平均粗さRaの下限は、特に制限されないが、例えば0.01μmとすればよい。
絶縁被膜形成工程では、平滑化された仕上げ焼鈍板の表面に、必要に応じて磁区制御処理を行った後、絶縁被膜を形成する。本実施形態では、絶縁被膜形成工程後の鋼板を、方向性電磁鋼板と呼ぶ。
本実施形態に係る方向性電磁鋼板の製造方法では、冷延工程と脱炭焼鈍工程との間(第1)、脱炭焼鈍工程と焼鈍分離剤塗布工程との間(第2)、平滑化工程と絶縁被膜形成工程との間(第3)、または絶縁被膜形成工程後(第4)のいずれかに、磁区制御処理を行う磁区制御工程を備えてもよい。
作製した方向性電磁鋼板から採取した試料に対し、JIS C 2550-1:2000に基づき、エプスタイン試験により励磁磁束密度1.7T、周波数50Hzにおける鉄損W17/50(W/kg)を測定した。磁区制御を行った方向性電磁鋼板については、鉄損W17/50が0.7W/kg未満の場合を合格と判断した。また、磁区制御を行わない方向性電磁鋼板については、鉄損W17/50が1.0W/kg未満の場合を合格と判断した。
製造した方向性電磁鋼板から採取した試験片を、直径20mmの円筒に巻き付け(180°曲げ)、曲げ戻した時の被膜残存面積率で、絶縁被膜の被膜密着性を評価した。絶縁被膜の被膜密着性の評価は、目視で絶縁被膜の剥離の有無を判断した。鋼板から剥離せず、被膜残存面積率が90%以上を◎(VERY GOOD)、85%以上90%未満を〇(GOOD)、80%以上85%未満を△(POOR)、80%未満を×(NG)とした。被膜残存面積率が85%以上の場合(上記の◎または〇)を合格と判断した。
その結果を表11~13に示す。
これに対し、比較例であるNo.b1~b31については、1つ以上の工程条件が本発明範囲を外れており、鉄損及び/または被膜密着性が劣っていた。なお、比較例No.b23については、圧延ができなかったので、それ以降の評価を行っていない。
Claims (6)
- 化学組成として、質量%で、
C:0.030~0.100%、
Si:0.80~7.00%、
Mn:0.01~1.00%、
S及びSeの合計:0~0.060%、
酸可溶性Al:0.010~0.065%、
N:0.004~0.012%、
Cr:0~0.30%、
Cu:0~0.40%、
P:0~0.50%、
Sn:0~0.30%、
Sb:0~0.30%、
Ni:0~1.00%、
B:0~0.008%、
V:0~0.15%、
Nb:0~0.20%、
Mo:0~0.10%、
Ti:0~0.015%、
Bi:0~0.010%、を含有し、
残部がFeおよび不純物からなる鋼片を、熱間圧延して熱延鋼板を得る熱延工程と、
前記熱延鋼板に冷間圧延を施して冷延鋼板を得る冷延工程と、
前記冷延鋼板に脱炭焼鈍を行って脱炭焼鈍板を得る脱炭焼鈍工程と、
前記脱炭焼鈍板に、Al2O3とMgOとを含有する焼鈍分離剤を塗布して乾燥させる焼鈍分離剤塗布工程と、
前記焼鈍分離剤が塗布された前記脱炭焼鈍板に仕上げ焼鈍を行い、仕上げ焼鈍板を得る仕上げ焼鈍工程と、
前記仕上げ焼鈍板の表面から余剰の焼鈍分離剤を除去する焼鈍分離剤除去工程と、
前記余剰の焼鈍分離剤が除去された前記仕上げ焼鈍板の表面を平滑化する平滑化工程と、
平滑化された前記仕上げ焼鈍板の表面に絶縁被膜を形成する絶縁被膜形成工程と、
を備え、
前記脱炭焼鈍工程では、
酸化度であるPH2O/PH2が0.18~0.80である雰囲気下で、焼鈍温度750~900℃で、10~600秒保持を行い、
前記焼鈍分離剤塗布工程では、
前記焼鈍分離剤における、前記MgOと前記Al2O3との質量比率であるMgO/(MgO+Al2O3)を5~50%、水和水分を1.5質量%以下とし、
前記仕上げ焼鈍工程では、
前記焼鈍分離剤が塗布された前記脱炭焼鈍板を、体積率で水素を50%以上含む混合ガス雰囲気中で、1100~1200℃の温度で10時間以上保持し、
前記焼鈍分離剤除去工程では、
前記仕上げ焼鈍板の表面から余剰の焼鈍分離剤を、トリエタノールアミン、ロジンアミン、またはメカプタンの少なくとも1つであるインヒビターを添加した溶液を用いて水洗して除去し、鋼板表面における鉄系水酸化物量及び鉄系酸化物量を片面当り0.9g/m2以下にし、
前記平滑化工程では、
化学研磨により、前記余剰の焼鈍分離剤が除去された前記仕上げ焼鈍板の表面を、平均粗さRaが0.1μm以下となるようにし、
前記絶縁被膜形成工程では、
リン酸塩、コロイダルシリカ、および結晶性燐化物を含む被膜形成溶液を塗布して350~1150℃で焼き付け、降温後に、リン酸塩およびコロイダルシリカを含むが結晶性燐化物を含まない被膜形成溶液を塗布して350~1150℃で焼き付けて絶縁被膜を形成する
ことを特徴とする方向性電磁鋼板の製造方法。 - 前記熱延工程と前記冷延工程との間に、
前記熱延鋼板を焼鈍する熱延板焼鈍工程、または酸洗を行う熱延板酸洗工程の少なくとも1つを備える
ことを特徴とする請求項1に記載の方向性電磁鋼板の製造方法。 - 前記脱炭焼鈍工程では、前記冷延鋼板を、アンモニアを含有する雰囲気中で焼鈍する窒化処理を行う
ことを特徴とする請求項1または2に記載の方向性電磁鋼板の製造方法。 - 前記冷延工程と前記脱炭焼鈍工程との間、前記脱炭焼鈍工程と前記焼鈍分離剤塗布工程との間、前記平滑化工程と前記絶縁被膜形成工程との間、または前記絶縁被膜形成工程後のいずれかに、磁区制御処理を行う磁区制御工程を備える
ことを特徴とする請求項1~3のいずれか一項に記載の方向性電磁鋼板の製造方法。 - 前記焼鈍分離剤除去工程では、前記水洗後に、体積比濃度が20%未満の酸性溶液を用いて酸洗を行う
ことを特徴とする請求項1~4のいずれか一項に記載の方向性電磁鋼板の製造方法。 - 前記鋼片が、化学組成として、質量%で、
Cr:0.02~0.30%、
Cu:0.05~0.40%、
P:0.005~0.50%、
Sn:0.02~0.30%、
Sb:0.01~0.30%、
Ni:0.01~1.00%、
B:0.0005~0.008%、
V:0.002~0.15%、
Nb:0.005~0.20%、
Mo:0.005~0.10%、
Ti:0.002~0.015%、及び
Bi:0.001~0.010%、
からなる群から選択される少なくとも1種を含有する
ことを特徴とする請求項1~5のいずれか一項に記載の方向性電磁鋼板の製造方法。
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- 2020-01-16 JP JP2020566455A patent/JP7269504B2/ja active Active
- 2020-01-16 US US17/421,802 patent/US11946113B2/en active Active
- 2020-01-16 CN CN202080008839.3A patent/CN113272454B/zh active Active
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Patent Citations (9)
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JPS4996920A (ja) | 1973-01-22 | 1974-09-13 | ||
JPS6479381A (en) * | 1987-06-10 | 1989-03-24 | Kawasaki Steel Co | Protective coating material for annealing |
JPH0347975A (ja) * | 1989-07-13 | 1991-02-28 | Kawasaki Steel Corp | 低鉄損一方向性珪素鋼板 |
JPH07278676A (ja) * | 1994-04-15 | 1995-10-24 | Nippon Steel Corp | 超低鉄損方向性電磁鋼板の製造法 |
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CN102952931A (zh) * | 2011-08-30 | 2013-03-06 | 宝山钢铁股份有限公司 | 一种无玻璃膜取向硅钢制造方法及退火隔离剂 |
JP2019005085A (ja) | 2017-06-22 | 2019-01-17 | サミー株式会社 | 回胴式遊技機 |
Also Published As
Publication number | Publication date |
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US11946113B2 (en) | 2024-04-02 |
JPWO2020149336A1 (ja) | 2021-11-25 |
CN113272454A (zh) | 2021-08-17 |
KR102583079B1 (ko) | 2023-10-04 |
EP3913081A4 (en) | 2022-10-05 |
KR20210111809A (ko) | 2021-09-13 |
US20220098689A1 (en) | 2022-03-31 |
EP3913081A1 (en) | 2021-11-24 |
BR112021013519A2 (pt) | 2021-09-14 |
CN113272454B (zh) | 2023-04-18 |
EP3913081B1 (en) | 2024-06-05 |
JP7269504B2 (ja) | 2023-05-09 |
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