WO2015064472A1 - 磁気特性および被膜密着性に優れる方向性電磁鋼板 - Google Patents
磁気特性および被膜密着性に優れる方向性電磁鋼板 Download PDFInfo
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- WO2015064472A1 WO2015064472A1 PCT/JP2014/078233 JP2014078233W WO2015064472A1 WO 2015064472 A1 WO2015064472 A1 WO 2015064472A1 JP 2014078233 W JP2014078233 W JP 2014078233W WO 2015064472 A1 WO2015064472 A1 WO 2015064472A1
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14766—Fe-Si based alloys
- H01F1/14775—Fe-Si based alloys in the form of sheets
- H01F1/14783—Fe-Si based alloys in the form of sheets with insulating coating
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0205—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips of ferrous alloys
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1244—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the heat treatment(s) being of interest
- C21D8/1272—Final recrystallisation annealing
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1283—Application of a separating or insulating coating
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
- C21D8/1288—Application of a tension-inducing coating
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
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- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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Definitions
- the present invention relates to a grain-oriented electrical steel sheet having excellent magnetic properties and coating adhesion.
- a grain-oriented electrical steel sheet is a soft magnetic material used as a core material for transformers, generators, etc., and has a crystal structure in which the ⁇ 001> orientation, which is the easy axis of iron, is highly aligned with the rolling direction of the steel sheet. It is a feature.
- Such a texture is a secondary re-growth that preferentially grows grains of the ⁇ 110 ⁇ ⁇ 001> orientation, so-called Goss orientation, in finish annealing in the production process of grain-oriented electrical steel sheets. Formed through crystal annealing.
- a coating layer mainly composed of oxides such as forsterite and a coating layer mainly composed of phosphate glass are formed from the steel sheet side.
- Phosphate-based glassy coatings are formed for the purpose of imparting insulating properties, workability, rust prevention properties, etc., but because glass and metal have low adhesion, they are mainly composed of oxides such as forsterite.
- the film adhesion is improved by interposing a ceramic layer between.
- Patent Document 2 has a film mainly composed of magnesium phosphate, colloidal silica and chromic anhydride
- Patent Document 3 has a film mainly composed of aluminum phosphate, colloidal silica and chromic anhydride. Proposed.
- Patent Document 4 discloses that the tension applied to the steel sheet is 8 MPa or less after specializing in direct ignition applications, and the forsterite layer and the inorganic insulating coating. A technique for improving the adhesion of a film by optimizing the basis weight ratio is disclosed.
- the recrystallization grain refinement is effective.
- a technique for refining secondary recrystallized grains there is a method of rapid heating by primary recrystallization annealing that also serves as primary recrystallization annealing or decarburization annealing, or rapid heating treatment immediately before primary recrystallization annealing.
- methods for improving the primary recrystallization texture have been developed.
- the atmospheric oxygen concentration is set to 500 ppm or less, and it is rapidly heated to a temperature of 800 to 950 ° C. at a heating rate of 100 ° C./s or more.
- Decarburization annealing is performed by setting the temperature in the front region of the decarburization annealing process to 775 to 840 ° C., which is lower than the temperature reached in the rapid heating, and the temperature in the subsequent rear region to 815 to 875 ° C.
- Patent Document 6 a technique for obtaining a grain-oriented electrical steel sheet having a low iron loss is disclosed in Patent Document 6, in which pH 2 O / pH 2 is 0.2 immediately before decarburizing and annealing a steel strip rolled to a final thickness.
- a technique for obtaining a grain-oriented electrical steel sheet with low iron loss by rapidly heating to a temperature of 700 ° C. or higher at a heating rate of 100 ° C./s or higher in the following non-oxidizing atmosphere is disclosed.
- Patent Document 7 discloses that a temperature range of at least 600 ° C. in the temperature rising stage of the decarburization annealing process is heated to 800 ° C. or higher at a temperature rising rate of 95 ° C./s or more, and an atmosphere in this temperature range is set.
- Patent Document 8 discloses that a temperature range of at least 650 ° C.
- a grain-oriented electrical steel sheet having excellent coating properties and magnetic properties can be obtained by using an inert gas and setting the ratio pH 2 O / pH 2 of the H 2 O partial pressure to the H 2 partial pressure to be 0.15 to 0.65. Obtaining techniques are disclosed.
- Japanese Patent Laid-Open No. 08-67913 Japanese Patent Publication No. 56-52117 Japanese Patent Application Laid-Open No. 50-79422
- Japanese Patent Publication No. 53-28375 Japanese Patent Laid-Open No. 48-393308
- JP 2002-60957 A Japanese Patent Laid-Open No. 10-298653 Japanese Patent Application Laid-Open No. 07-62436 JP 2003-27194 A Japanese Patent No. 3537339 (Japanese Patent Laid-Open No. 11-8294)
- the magnetic properties can be improved by the refinement of secondary recrystallized grains, and the coating properties can be improved. It has been planned. However, no matter how the above techniques are combined, there are some cases where the film properties, particularly the film adhesion, are inferior.
- the present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to have stable magnetic properties and coating adhesion even when rapid heating is performed in primary recrystallization annealing (decarburization annealing). It is in providing the grain-oriented electrical steel sheet which is excellent in.
- the inventors mainly have a surface layer of a grain-oriented electrical steel sheet mainly composed of an oxide layer formed on the steel sheet side and a glassy material formed on the surface side. Paying attention to the fact that it is composed of two coating layers of the coating layer, intensive studies were conducted on measures for improving the coating adhesion. As a result, the ratio of the tension applied to the steel sheet by the coating layer mainly composed of oxide formed on the steel sheet side and the tension applied to the steel sheet by the coating layer mainly composed of vitreous formed on the surface side should be optimized. Thus, the inventors have found that not only the magnetic properties are excellent, but also the adhesion between the steel sheet side coating layer and the steel sheet can be greatly improved, and the present invention has been completed.
- the present invention has a tension composed of two layers of a coating layer A mainly composed of an oxide formed on the steel plate side and a coating layer B mainly composed of vitreous formed on the surface side.
- the ratio R ( ⁇ B / ⁇ A ) of the tension ⁇ B applied to the steel sheet by the surface side coating layer B to the tension ⁇ A applied to the steel sheet by the steel sheet side coating layer A is 1 It is a grain-oriented electrical steel sheet characterized by being in the range of 20 to 4.0.
- the oxide of the steel sheet side coating layer A in the grain-oriented electrical steel sheet of the present invention is forsterite, and the glassy material of the surface side coating layer B is Mg, Al, Ca, Ti, Nd, Mo, Cr, B, Ta, It is a silicic acid glass containing one or more metal elements selected from Cu and Mn.
- the grain-oriented electrical steel sheet according to the present invention is characterized in that the tension ⁇ A applied to the steel sheet by the steel sheet-side coating layer A is 6 MPa or less.
- the basis weight of the steel sheet-side coating layer A is 1.0 to 3.0 g / m 2 (both sides) in terms of oxygen.
- the grain-oriented electrical steel sheet according to the present invention is obtained by subjecting a cold-rolled sheet rolled to a final sheet thickness to a secondary recrystallization annealing after heating at a temperature increase rate of 50 ° C./s or more between 100 to 700 ° C. It is obtained by recrystallization annealing.
- the main component is oxide. It is possible to stably produce a grain-oriented electrical steel sheet with excellent magnetic properties and coating properties simply by controlling the tension ratio given to the steel plate by the steel sheet-side coating layer and the glass-side surface-side coating layer. It becomes possible.
- the technology to refine the secondary recrystallized grains by performing rapid heating in the primary recrystallization annealing is a very excellent technology to improve the magnetic properties, but greatly affects the initial oxidation state of the steel sheet surface, In particular, the density of the internal oxide layer formed by decarburization annealing is lowered, and the density of the ceramic coating formed during secondary recrystallization annealing and thus the adhesion to the steel sheet are adversely affected. Is caused.
- the grain-oriented electrical steel sheet according to the present invention includes two coating layers, A film layer A mainly composed of an oxide formed on the steel sheet side and a film layer B mainly composed of vitreous formed on the surface side.
- the ratio of the tension ⁇ B applied to the steel sheet by the surface side coating layer B to the tension ⁇ A applied to the steel sheet by the steel sheet side coating layer A (Tension ratio) R ( ⁇ B / ⁇ A ) needs to be in the range of 1.20 to 4.0.
- the tension ratio R is preferably in the range of 1.4 to 3.0.
- the tension applied to the steel sheet by the coating on the steel sheet surface is the tension in the rolling direction
- the measurement method of the magnitude is the warpage of the steel sheet when the coating on one side of the steel sheet is removed using alkali or acid. From the size, it can be calculated using the following formula.
- the steel sheet-side coating layer mainly composed of oxide in the grain-oriented electrical steel sheet of the present invention is preferably a ceramic layer such as forsterite or cordierite, and among these, forsterite is preferable. This is because an oxide film mainly composed of forsterite can be manufactured at a low cost by a method in which an annealing separator mainly composed of MgO is applied after decarburization annealing and finish annealing is performed.
- the surface side coating layer mainly composed of vitreous is preferably made of silicic acid glass.
- the silicic acid-based glass is one kind selected from Mg, Al, Ca, Ti, Nd, Mo, Cr, B, Ta, Cu and Mn for the purpose of improving water resistance, which is a drawback. Or it is preferable that 2 or more types of metal elements are contained.
- the tension ⁇ A that the steel sheet-side coating layer imparts to the steel sheet is preferably 6 MPa or less. This is because when the pressure is 6 MPa or less, the stress between the steel sheet and the steel sheet-side coating layer is relatively small, so that the critical stress value at which peeling occurs also in the bending peel test increases, and the film adhesion improves.
- the tension ⁇ A is preferably 1.0 MPa or more. More preferably, it is in the range of 1.5 to 4.0 MPa.
- the basis weight of the steel sheet side coating layer (layer mainly composed of oxide) in the grain-oriented electrical steel sheet of the present invention is preferably in the range of 1.0 to 3.0 g / m 2 in terms of oxygen.
- the steel sheet coverage of the coating layer is sufficiently high, and even if a surface side coating layer mainly composed of glass is formed, the coating layer has excellent uniformity in appearance. can get.
- the thickness of the steel sheet-side coating layer is so thin that the coating adhesion is excellent. More preferably, it is in the range of 1.5 to 3.0 g / m 2 .
- the grain-oriented electrical steel sheet targeted by the present invention is usually manufactured by a known method, and on the steel sheet surface, a steel sheet side coating layer mainly composed of oxide and a surface side mainly composed of glass. Any one having two coating layers can be used, but the steel sheet is preferably produced by the method described below.
- a steel material (slab) as a material of the grain-oriented electrical steel sheet of the present invention has the following component composition C: 0.001 to 0.10 mass%
- C is a component useful for generating goth-oriented grains, and is preferably contained in an amount of 0.001 mass% or more in order to effectively exhibit such an effect.
- C is preferably in the range of 0.001 to 0.10 mass%. More preferably, it is in the range of 0.010 to 0.08 mass%.
- Si 1.0 to 5.0 mass%
- Si is a component necessary for increasing the electrical resistance of steel and reducing iron loss, stabilizing the BCC structure of iron, and enabling heat treatment at high temperature, and is added at least 1.0 mass%. Is preferred. However, addition exceeding 5.0 mass% makes it difficult to cold-roll. Therefore, Si is preferably in the range of 1.0 to 5.0 mass%. More preferably, it is in the range of 2.0 to 4.5 mass%.
- Mn 0.01 to 1.0 mass% Mn not only effectively contributes to the improvement of hot brittleness of steel, but when S and Se are mixed, precipitates such as MnS and MnSe are formed and function as an inhibitor (inhibitor). To do. If the Mn content is less than 0.01 mass%, the above effect is insufficient. On the other hand, if the Mn content exceeds 1.0 mass%, the particle size of precipitates such as MnSe becomes coarse and the effect as an inhibitor is lost. Is called. Therefore, Mn is preferably in the range of 0.01 to 1.0 mass%. More preferably, it is in the range of 0.015 to 0.80 mass%.
- Al 0.003 to 0.050 mass%
- Al is a useful component that forms AlN in steel and becomes a dispersed second phase and acts as an inhibitor. However, if the addition amount is less than 0.003 mass%, a sufficient precipitation amount of AlN cannot be secured, On the other hand, if added over 0.050 mass%, AlN precipitates coarsely and the action as an inhibitor is lost. Therefore, Al is sol.
- a range of 0.003 to 0.050 mass% with Al is preferable. More preferably, it is in the range of 0.005 to 0.045 mass%.
- N 0.001 to 0.020 mass%
- N is a component necessary for forming AlN. If the addition amount is less than 0.001 mass%, the precipitation of AlN becomes insufficient. On the other hand, if the addition amount exceeds 0.020 mass%, blistering or the like occurs during reheating of the slab, causing surface defects. Therefore, N is preferably in the range of 0.001 to 0.020 mass%. More preferably, it is in the range of 0.002 to 0.015 mass%.
- One or two selected from S and Se: 0.001 to 0.05 mass% in total S and Se are useful components that combine with Mn and Cu to form MnSe, MnS, Cu 2-X Se, Cu 2-X S, become a dispersed second phase in steel, and exert an inhibitor action. . If the total content of S and Se is less than 0.001 mass%, the above effect is poor. On the other hand, if it exceeds 0.05 mass%, not only the solid solution during reheating of the slab becomes insufficient, but also the product plate Cause surface defects. Therefore, in either case of single addition or composite addition, the total content is preferably in the range of 0.01 to 0.05 mass%. More preferably, it is in the range of 0.015 to 0.045 mass%.
- the steel material used for the grain-oriented electrical steel sheet of the present invention is further Cu: 0.01-0.2 mass%, Ni: 0.01-0.5 mass%, Cr: 0.01-0. 5 mass%, Sb: 0.01-0.1 mass%, Sn: 0.01-0.5 mass%, Mo: 0.01-0.5 mass% and Bi: 0.001-0.1 mass% 1 type, or 2 or more types can be contained.
- the above-mentioned elements are easily segregated on the crystal grain size and the surface, and have an action as an auxiliary inhibitor. Therefore, the addition of these elements makes it possible to further improve the magnetic properties. However, if any element is less than the above-mentioned addition amount, the above-described addition effect cannot be obtained. On the other hand, if the amount exceeds the above-mentioned amount, the appearance of the film and the secondary recrystallization are likely to occur. Therefore, when it is added, the above range is preferable.
- the steel material used for the grain-oriented electrical steel sheet of the present invention is further B: 0.001 to 0.01 mass%, Ge: 0.001 to 0.1 mass%, As: 0.005 to 0.1 mass%, P: 0.005 to 0.1 mass%, Te: 0.005 to 0.1 mass%, Nb: 0.005 to 0.1 mass%, Ti: 0.005 to 0.1 mass%, and V : One or more selected from 0.005 to 0.1 mass% can be contained.
- the inhibitory power of the inhibitor is further strengthened, and a higher magnetic flux density can be stably obtained.
- the grain-oriented electrical steel sheet of the present invention is a steel material (slab) obtained by melting a steel having the above-described composition by a conventional refining process and using a continuous casting method or an ingot-bundling rolling method. After that, the slab is hot-rolled to obtain a hot-rolled sheet, which is subjected to hot-rolled sheet annealing or not, and then cold-rolled sheet having a final thickness by one or more cold rollings sandwiching intermediate annealing.
- an annealing separator mainly composed of MgO is applied to the steel sheet surface, dried, wound into a coil, and then finished. It is possible to manufacture by a manufacturing method consisting of a series of steps that undergo annealing and forming a film layer mainly composed of forsterite, and further undergoing flattening annealing that combines application of baking, baking and shape correction. it can. Conventionally known conditions can be employed for the production conditions other than the primary recrystallization annealing (decarburization annealing) and the annealing separator applied to the steel sheet surface before the finish annealing, and there is no particular limitation.
- the primary recrystallization annealing also serving as the primary recrystallization annealing or the decarburization annealing
- the ratio of Goss orientation in the primary recrystallization texture can be increased, and the number of Goss grains after secondary recrystallization can be increased to reduce the average grain size.
- the rate of temperature increase becomes too fast, the amount of ⁇ lll ⁇ structure phagocytosed in the Goss orientation ⁇ 110 ⁇ ⁇ 001> decreases and secondary recrystallization failure tends to occur.
- the range is preferably 80 to 250 ° C./s.
- the temperature range for rapid heating by primary recrystallization annealing is preferably between 100 and 700 ° C. Since the temperature at which the steel sheet reaches the annealing furnace varies depending on the outside air temperature, the processing temperature in the previous process, the conveying time of the steel sheet, and the like, control from 100 ° C. becomes easy. On the other hand, even if the temperature at which rapid heating is terminated exceeds 700 ° C. at which primary recrystallization starts, not only is the effect of rapid heating saturated, but also the energy cost required for rapid heating increases, which is not preferable.
- C in a steel plate may be less than 0.0050 mass%. Therefore, it is not necessarily performed when C of the steel material (slab) is less than 0.0050 mass%.
- the decarburization annealing may be performed separately without performing the primary recrystallization annealing. However, when the decarburization annealing is performed first, it is necessary to perform rapid heating by the decarburization annealing.
- the annealing separator applied to the steel sheet surface after primary recrystallization annealing and before finish annealing is mainly composed of MgO in order to form a coating layer mainly composed of oxides such as forsterite and cordierite. It is preferable to use an annealing separator which is a component or contains MgO.
- the oxygen basis weight of the coating on the steel sheet surface is preferably in the range of 1.0 to 3.0 g / m 2 .
- the primary recrystallization annealing was performed, which was also heated up to 820 ° C. at a temperature rising rate of 20 ° C./s, and also served as decarburization annealing for decarburization in a humid atmosphere. At that time, the primary recrystallization annealing time was variously changed as described in Table 1, and the oxygen basis weight on the steel sheet surface after annealing was changed.
- an annealing separator in which 10 parts by weight of TiO 2 is mixed with 100 parts by weight of MgO is applied in a water slurry, dried, and then heated between 300 ° C. and 800 ° C. over 100 hours, and then 1200 After the temperature was raised to 50 ° C. at 50 ° C./hr to complete the secondary recrystallization, finish annealing was performed by purifying by holding at 1200 ° C. for 5 hours.
- the coating solution for insulation tension coating silicotungstic phosphate-based compositions containing CrO 3 10 mol% of magnesium phosphate as Mg (PO 3) 2 And baked at 850 ° C. for 1 minute. At that time, the tension applied to the steel sheet by the insulating tension coating was changed by changing the coating weight per unit area.
- the forsterite coating (steel-side coating layer) and the vitreous coating (surface-side coating layer) applied to the steel plate with the tension ( ⁇ A , ⁇ B ) and the magnetizing force of 800 A / m.
- the film peeling test (bending peeling test) after measuring the iron loss W 17/50 at a magnetic flux density of B 8 , 1.7 T, 50 Hz and performing strain relief annealing in a nitrogen atmosphere at 800 ° C. for 3 hours. The results were measured and the results are shown in Table 1.
- a test piece having a width of 100 mm and a length of 400 mm was taken from the same cold plate as used in Example 1, and in a laboratory, in a humid atmosphere, at a heating rate of 100 ° C. to 700 ° C. at a temperature rising rate described in Table 2. Then, the temperature was further increased to 850 ° C. at 20 ° C./s, and primary recrystallization annealing was performed which also served as decarburization annealing for maintaining soaking for 120 s. Next, an annealing separator containing Al 2 O 3 and MgO at a mass ratio of 3: 2 was applied to the surface of the test piece in a water slurry and dried. Next, the test piece was heated between 300 ° C.
- the film was made of cordierite (2MgO ⁇ 2Al 2 O 3 ⁇ 5SiO 2 ) on the surface of the steel plate by performing finish annealing for purifying the steel.
- the basis weight of the film in terms of oxygen was 2.0 g / m 2 , and the tension applied to the steel sheet was 4.0 MPa.
- the forsterite coating (steel-side coating layer) and the vitreous coating (surface-side coating layer) applied to the steel plate with the tension ( ⁇ A , ⁇ B ) and the magnetizing force of 800 A / m.
- the film peeling test (bending peeling test) after measuring the iron loss W 17/50 at a magnetic flux density of B 8 , 1.7 T, 50 Hz and performing strain relief annealing in a nitrogen atmosphere at 800 ° C. for 3 hours. Measurements were made and the results are shown in Table 2.
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Abstract
Description
鋼板への付与張力(MPa)=(鋼板のヤング率(GPa))×板厚(mm)×反りの大きさ(mm)÷(反りの測定試験片長さ(mm))2×103
(ただし、上記鋼板のヤング率は132GPaを用いる。)
なお、被膜が2層からなる場合のそれぞれの被膜の張力は、まず、最外層(B層)のみを除去して反りを測定し、この反りからB層の張力を算出し、次いで、内層(A層)を除去して反りを測定し、この反りから(A層+B層)の張力を算出し、上記B層と(A層+B層)の張力の差分を、内層(A層)の張力とすることで測定する。
C:0.001~0.10mass%
Cは、ゴス方位粒を発生させるのに有用な成分であり、斯かる効果を有効に発現させるためには、0.001mass%以上含有させることが好ましい。しかし、0.10mass%を超えると、後工程の脱炭焼鈍で、磁気時効を起こさないレベル(0.005mass%以下)まで脱炭することが難しくなる。よって、Cは0.001~0.10mass%の範囲とするのが好ましい。より好ましくは0.010~0.08mass%の範囲である。
Siは、鋼の電気抵抗を高めて鉄損を低下させるとともに、鉄のBCC組織を安定化させ、高温での熱処理を可能とするために必要な成分であり、少なくとも1.0mass%添加するのが好ましい。しかし、5.0mass%を超える添加は、冷間圧延することが困難となる。よって、Siは1.0~5.0mass%の範囲とするのが好ましい。より好ましくは2.0~4.5mass%の範囲である。
Mnは、鋼の熱間脆性の改善に有効に寄与するだけでなく、SやSeが混在しているときには、MnSやMnSe等の析出物を形成し、抑制剤(インヒビター)としての機能を発揮する。Mnの含有量が0.01mass%より少ないと、上記の効果が不十分となり、一方、1.0mass%を超えると、MnSe等の析出物の粒径が粗大化して、インヒビターとしての効果が失われる。よって、Mnは0.01~1.0mass%の範囲とするのが好ましい。より好ましくは0.015~0.80mass%の範囲である。
Alは、鋼中でAlNを形成して分散第二相となり、インヒビターとして作用する有用成分であるが、添加量が0.003mass%に満たないと、AlNの析出量が十分に確保できず、一方、0.050mass%を超えて添加すると、AlNが粗大に析出してインヒビターとしての作用が失われる。よって、Alは、sol.Alで0.003~0.050mass%の範囲とするのが好ましい。より好ましくは0.005~0.045mass%の範囲である。
Nは、Alと同様、AlNを形成するために必要な成分である。添加量が0.001mass%を下回ると、AlNの析出が不十分となり、一方、0.020mass%を超えて添加すると、スラブ再加熱時にふくれ等を生じて表面欠陥の発生原因となる。よって、Nは0.001~0.020mass%の範囲とするのが好ましい。より好ましくは0.002~0.015mass%の範囲である。
SおよびSeは、MnやCuと結合してMnSe,MnS,Cu2-XSe,Cu2-XSを形成して鋼中の分散第二相となり、インヒビターの作用を発揮する有用成分である。SおよびSeの合計含有量が0.001mass%に満たないと、上記効果に乏しく、一方、0.05mass%を超えると、スラブ再加熱時の固溶が不十分となるだけでなく、製品板の表面欠陥の原因ともなる。よって、単独添加または複合添加のいずれの場合においても合計で0.01~0.05mass%の範囲とするのが好ましい。より好ましくは0.015~0.045mass%の範囲である。
本発明の方向性電磁鋼板は、上記に説明した成分組成を有する鋼を常法の精錬プロセスで溶製し、連続鋳造法または造塊-分塊圧延法を用いて鋼素材(スラブ)とした後、上記スラブを熱間圧延して熱延板とし、熱延板焼鈍を施しあるいは施さず、その後、1回もしくは中間焼鈍を挟む1回以上の冷間圧延により最終板厚の冷延板とし、一次再結晶焼鈍あるいは脱炭焼鈍を兼ねた一次再結晶焼鈍を施した後、例えば、MgOを主成分とする焼鈍分離剤を鋼板表面に塗布し、乾燥し、コイルに巻き取った後、仕上焼鈍を施してフォルステライトを主体とする被膜層を形成し、さらに、ガラス質の絶縁被膜の塗布、焼付けと形状矯正を兼ねた平坦化焼鈍を経る一連の工程からなる製造方法で製造することができる。上記一次再結晶焼鈍(脱炭焼鈍)、および、仕上焼鈍前に鋼板表面に塗布する焼鈍分離剤以外の製造条件については、従来公知の条件を採用することができ、特に制限はない。
Claims (5)
- 鋼板表面に、鋼板側に形成された酸化物を主体とする被膜層Aと、表面側に形成されたガラス質を主体とする被膜層Bの2層から構成される張力付与型絶縁被膜を有する方向性電磁鋼板において、
上記鋼板側被膜層Aが鋼板に与える張力σAに対する表面側被膜層Bが鋼板に与える張力σBの比R(σB/σA)が1.20~4.0の範囲にあることを特徴とする方向性電磁鋼板。 - 鋼板側被膜層Aの酸化物はフォルステライトであり、表面側被膜層Bのガラス質はMg,Al,Ca,Ti,Nd,Mo,Cr,B,Ta,CuおよびMnのうちから選ばれる1種または2種以上の金属元素を含有する珪リン酸塩系ガラスであることを特徴とする請求項1に記載の方向性電磁鋼板。
- 鋼板側被膜層Aが鋼板に与える張力σAが6MPa以下である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。
- 鋼板側被膜層Aの目付量が酸素換算で1.0~3.0g/m2(両面)であることを特徴とする請求項1~3のいずれか1項に記載の方向性電磁鋼板。
- 最終板厚に圧延した冷延板を、100~700℃の間を昇温速度50℃/s以上で加熱する一次再結晶焼鈍した後、二次再結晶焼鈍して得たものであることを特徴とする請求項1~4のいずれか1項に記載の方向性電磁鋼板。
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JP7393623B2 (ja) * | 2019-09-19 | 2023-12-07 | 日本製鉄株式会社 | 方向性電磁鋼板 |
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KR102597512B1 (ko) * | 2020-12-22 | 2023-11-01 | 주식회사 포스코 | 방향성 전기강판 및 그의 제조방법 |
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RU2016121005A (ru) | 2017-12-05 |
US10395807B2 (en) | 2019-08-27 |
KR20160044561A (ko) | 2016-04-25 |
KR101763085B1 (ko) | 2017-07-28 |
EP3064607B1 (en) | 2018-02-21 |
EP3064607A1 (en) | 2016-09-07 |
RU2639178C2 (ru) | 2017-12-20 |
CN105593393A (zh) | 2016-05-18 |
US20160260531A1 (en) | 2016-09-08 |
JP6156646B2 (ja) | 2017-07-05 |
JP2015086426A (ja) | 2015-05-07 |
EP3064607A4 (en) | 2016-09-07 |
CN105593393B (zh) | 2018-06-19 |
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