WO2020149328A1 - 一方向性電磁鋼板およびその製造方法 - Google Patents
一方向性電磁鋼板およびその製造方法 Download PDFInfo
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- WO2020149328A1 WO2020149328A1 PCT/JP2020/001156 JP2020001156W WO2020149328A1 WO 2020149328 A1 WO2020149328 A1 WO 2020149328A1 JP 2020001156 W JP2020001156 W JP 2020001156W WO 2020149328 A1 WO2020149328 A1 WO 2020149328A1
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- steel sheet
- spinel
- annealing
- insulating film
- steel plate
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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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- C23C22/00—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
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- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
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- C21D2201/00—Treatment for obtaining particular effects
- C21D2201/05—Grain orientation
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Definitions
- the present invention relates to a grain-oriented electrical steel sheet and a method for manufacturing the same.
- the present application claims priority based on Japanese Patent Application No. 2019-005131 filed in Japan on January 16, 2019, the content of which is incorporated herein.
- Unidirectional electrical steel sheet (unidirectional silicon steel sheet) is often used as an iron core material for transformers.
- the transformer is continuously used for a long time from installation to disposal, and continues to generate energy loss. Therefore, as an iron core material, a material with less iron loss is required in order to reduce energy loss. Applying tension to the steel sheet is effective for reducing iron loss. Therefore, it has been attempted to reduce iron loss by forming a film made of a material having a smaller thermal expansion coefficient than that of a steel sheet at a high temperature and applying tension generated during cooling to the steel sheet due to the difference in the thermal expansion coefficient.
- the film as described above there is a forsterite film formed by the reaction between the oxide on the surface of the steel sheet and the annealing separating agent containing MgO in the finish annealing step.
- the forsterite film can give tension to the steel sheet and has excellent film adhesion.
- the general method for producing unidirectional silicon steel sheet is to leave the forsterite film generated in the finish annealing process and then form the insulating film mainly containing phosphate.
- Patent Document 1 in order to apply a tension to a steel sheet to reduce iron loss, a coating liquid mainly containing colloidal silica and a phosphate is applied on the forsterite film and baked.
- the method of forming an insulating film by this is disclosed.
- Patent Document 3 discloses a method in which alumina having a purity of 99% or more and a particle size of 100 mesh to 400 mesh is used as an annealing separator.
- Patent Document 4 discloses a method using an annealing separator mainly composed of aluminum hydroxide.
- Patent Document 5 discloses a method of using an annealing separator in which an alkali metal compound containing a boric acid component is added to alumina.
- Patent Document 6 discloses a method in which an annealing separator containing 5 to 40% of hydrous silicate mineral powder and the balance being alumina.
- Patent Document 7 discloses an annealing separator containing 0.2 to 20% of strontium and barium compounds, 2 to 30% of calcia and calcium hydroxide, and the balance of alumina, in addition to hydrous silicate mineral powder. The technique used is disclosed.
- Patent Document 8 also discloses a method in which coarse-grained alumina having an average particle diameter of 1 ⁇ m to 50 ⁇ m is mixed with fine-grained alumina having an average particle diameter of 1 ⁇ m or less.
- Patent Document 9 discloses an annealing separator containing 15 to 70 parts by weight of inert magnesia having a specific surface area of 0.5 to 10 m 2 /g calcinated at 1300° C. or more and pulverized with respect to 100 parts by weight of alumina. It is disclosed.
- the decarburization annealed sheet is subjected to finish annealing by applying the above-mentioned technology, some effect can be recognized in preventing the formation of forsterite film. However, it was difficult to stably obtain a finish-annealed plate in which no forsterite film was formed and no oxide remained.
- Patent Document 10 discloses a method for stably obtaining a finish-annealed plate in which a forsterite film is not formed and no oxide remains.
- a powder made of alumina and unavoidable impurity elements having a calcination temperature of 900 to 1400° C. and a ⁇ ratio of 0.001 to 2.0 as an annealing separator, the residual oxide It is described that can be suppressed.
- Patent Document 10 With the method disclosed in Patent Document 10, it is possible to stably obtain a finish-annealed plate in which a forsterite film is not formed and no oxide remains. However, the method of Patent Document 10 does not form a forsterite coating and makes the surface of the steel sheet smooth, so there is room for improvement in the adhesion of the insulating coating.
- Patent Document 11 a tension-imparting insulating film and a unidirectional silicon steel plate are provided so that sufficient film adhesion can be obtained for a finish-annealed unidirectional silicon steel plate having no inorganic mineral film.
- a method of forming an external oxidation type oxide film made of silica having a film thickness of 2 nm or more and 500 nm or less on the interface is disclosed.
- the present invention is a unidirectional electrical steel sheet that does not have a forsterite-based coating on the surface of the steel sheet in order to significantly reduce iron loss, and the adhesion between the insulating coating and the steel sheet. It is an object of the present invention to provide an excellent grain-oriented electrical steel sheet and a method for manufacturing the same.
- the forsterite coating is effective for imparting tension to the steel sheet, but on the other hand, it also has the aspect of reducing the iron loss improving effect due to the coating tension. Therefore, in order to further improve the iron loss, it is preferable to form an insulating film that imparts tension on a steel sheet that does not have a forsterite film on its surface. However, when there is no forsterite film on the surface of the steel sheet, the film adhesion of the insulating film decreases.
- the present invention was made based on the above findings.
- the gist of the present invention is as follows. (1) A steel plate, an insulating film disposed on the steel plate, and a spinel that is inserted into the insulating film at a part of the steel plate at an interface between the steel plate and the insulating film.
- the grain-oriented electrical steel sheet, wherein the amount of the spinel is 5 to 50 mg/m 2 per unit area of the surface of the steel sheet.
- the grain-oriented electrical steel sheet of the present invention does not have a forsterite coating on the steel sheet surface, excellent magnetic properties can be obtained. Further, since there is a spinel (convex spinel) formed by being fitted into the insulating film at the interface between the steel plate and the insulating film, the adhesion between the steel plate and the insulating film is excellent. Further, according to the method for producing a unidirectional electrical steel sheet of the present invention, it is possible to provide a unidirectional electrical steel sheet having excellent magnetic properties and coating adhesion.
- FIG. 1 It is a schematic diagram which shows the grain-oriented electrical steel sheet which concerns on this embodiment. It is an example of a wide-angle X-ray diffraction chart of the unidirectional electrical steel sheet according to the present embodiment (a wide-angle X-ray diffraction chart (2 examples) showing that the product on the surface of the steel sheet is spinel). It is the example which observed the section of the grain-oriented electrical steel sheet concerning this embodiment with an optical microscope.
- the grain-oriented electrical steel sheet 1 according to the present embodiment has a steel sheet 2, an insulating film 4 formed on the steel sheet 2, and a part of an interface between the steel sheet 2 and the insulating film 4. , And the spinel 3 formed by being fitted into the insulating film 4.
- the annealing separator containing Al 2 O 3 and MgO is applied before the finish annealing, and the forsterite film is not formed between the steel plate 2 and the insulating film 4.
- the spinel 3 is formed at a part of the interface between the steel plate 2 and the insulating film 4, no intermediate layer such as an oxide film is formed.
- each of the steel plate 2, the spinel 3, and the insulating film 4 included in the unidirectional electromagnetic steel plate 1 according to this embodiment will be described in detail.
- the components of the steel sheet 2 are not particularly limited as long as they are in the range applicable to a normal unidirectional electrical steel sheet.
- a steel sheet having a chemical composition that can obtain preferable properties as a unidirectional electrical steel sheet after forming an insulating film for example, C: 0.085% or less, Si: 0.80 to 7.00%, Mn: 1 0.00% or less, Al: 0.065% or less, S: 0.013% or less, Cu: 0 to 0.80%, N: 0 to 0.012%, P: 0 to 0.5%, Ni:
- Examples of the steel sheet include 0 to 1.0%, Sn: 0 to 0.3%, Sb: 0 to 0.3%, and the balance being Fe and impurities.
- the above components of the steel plate 2 may be measured by a general steel analysis method.
- the components of the steel sheet 2 may be measured using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometry).
- C and S may be measured by a combustion-infrared absorption method, and N may be measured by an inert gas melting-thermal conductivity method.
- a part of the surface of the steel sheet 2 at the interface between the steel sheet 2 and the insulating film 4 is identified by a JCPDS (Joint Commitee on) which is identified from a diffraction pattern by a wide-angle X-ray diffraction method.
- the Powder Diffraction Standards) number is 21-1152, and the spinel 3 represented by MgAl 2 O 4 is formed.
- the spinel 3 is formed so as to adhere to the surface of the steel plate 2 and project from the steel plate 2 toward an insulating film 4 formed later.
- the spinel 3 is formed so as to fit into the insulating film 4.
- the fitting means that the spinel 3 enters the insulating film 4 from the interface between the insulating film 4 and the steel plate 2 in the plate thickness direction of the steel plate 2, as shown in FIG. 1.
- the spinel 3 is not fitted on the steel sheet 2 side.
- the spinel 3 thus formed may be referred to as “convex spinel”.
- FIG. 2 is an example of a wide-angle X-ray diffraction chart of the grain-oriented electrical steel sheet according to the present embodiment.
- the spinel 3 (convex spinel) is formed on the surface of the steel sheet 2 as described above. By doing so, the adhesion of the insulating film 4 can be enhanced.
- the spinel 3 (convex spinel) needs to be present in an amount of 5 to 50 mg/m 2 per unit area of the surface of the steel plate 2.
- the amount of spinel 3 (convex spinel) per unit area on the surface of the steel plate 2 exceeds 50 mg/m 2 , the spinel 3 is also fitted and formed inside the steel plate 2. In this case, iron loss increases (deteriorates). Therefore, the amount of spinel 3 (convex spinel) is set to 5 to 50 mg/m 2 per side of the steel sheet.
- the spinel 3 is formed by applying a decarburization-annealed steel sheet with an annealing separator containing MgO and Al 2 O 3 containing a ⁇ phase and an ⁇ phase, and then performing finish annealing, as described below. It An intermediate steel plate having the steel plate 2 and the spinel 3 formed on a part of the steel plate 2 by finish annealing, and the content of the spinel 3 being 5 to 50 mg/m 2 is obtained. Further, by forming the insulating film 4 on this intermediate steel plate, the unidirectional electromagnetic steel plate 1 according to the present embodiment is obtained.
- the content of the spinel 3 per unit area on the surface of the steel sheet 2 can be determined by the following method. First, the steel plate 2 having the spinel 3 and the insulating film 4 is immersed in a 40% sodium hydroxide aqueous solution heated to 85° C. for 20 minutes. Then, the surface of the steel sheet is wiped with a waste cloth under running water, and then thoroughly washed with running water. Finally, pass through a drier to dry the water. By these series of operations, the insulating film 4 is removed, and the steel plate 2 and the spinel 3 on the steel plate 2 remain.
- the crystal phase is identified by the wide-angle X-ray diffraction method, and the existence of alumina is not confirmed, but it is confirmed that the spinel 3 is generated.
- the residue on the surface of the steel sheet 2 was collected by a chemical dissolution method using a Br 2 /CH 3 OH solution, etc. After preparing a uniform solution in which is dissolved, the amount of Al 2 O 3 is calculated by the ICP method.
- the steel plate 2 does not have an Al 2 O 3 component other than the spinel 3, the content of the spinel 3 per unit area of the surface of the steel plate 2 can be obtained by the above method.
- the alumina caused an obstacle to the movement of the domain wall, which increased the iron loss, the presence of the alumina increased the amount of the insulating film, and the unevenness of the surface of the steel sheet 2.
- the presence or absence of alumina can be determined by the wide-angle X-ray diffraction method as described above.
- alumina is confirmed when the annealing separator mainly composed of alumina does not contain MgO or when the ratio of the weight of MgO to the total weight of Al 2 O 3 and MgO is less than 5%. This is the case. In such a case, since the alumina contained in the annealing separator seizes on the steel sheet, even if the steel sheet after finish annealing is washed with water or pickled, the alumina cannot be removed and the alumina remains on the steel sheet surface. To do.
- the existence form of the spinel 3 can be determined from an optical microscope image of a cross section in the plate thickness direction. Specifically, the steel plate 2 having the spinel 3 and the insulating film 4 is immersed in a 40% concentration aqueous sodium hydroxide solution heated to 85° C. for 20 minutes. Then, the surface of the steel sheet is wiped with a waste cloth under running water, and then thoroughly washed with running water. Finally, pass through a drier to dry the water. By these series of operations, the insulating film 4 is removed, and the steel plate 2 and the spinel 3 on the steel plate 2 remain.
- An observation sample is taken from the steel plate 2 having the spinel 3 so that the cross section in the plate thickness direction becomes the observation surface, and the observation surface is polished.
- An image of the polished sample is collected with an optical microscope at a magnification of about 1000 times.
- the steel plate 2 shows metal reflection
- the spinel 3 does not show metal reflection and appears black. From the observed image, if the black-colored spinel 3 exists on the outer side of the steel plate 2 that exhibits metal reflection, it can be determined that the spinel 3 is formed by being inserted into (entering) the insulating film 4. ..
- the insulating film 4 is formed on the steel plate 2.
- the insulating film 4 is formed on the spinel 3 in that part. That is, the insulating film 4 is formed on the steel plate 2 and the spinel 3.
- the insulating film 4 is an insulating film formed by applying and baking a coating liquid mainly containing phosphate and colloidal silica (SiO 2 ). With this insulating film 4, a strong surface tension can be applied to the steel plate 2 as the base material.
- the unidirectional electrical steel sheet 1 according to this embodiment does not require a step for forming a SiO 2 film, and is therefore preferable in terms of productivity.
- the unidirectional electrical steel sheet 1 according to this embodiment does not have a forsterite coating on the steel sheet 2.
- the presence or absence of the forsterite coating on the steel sheet 2 can be confirmed by analyzing the surface of the steel sheet from which the insulating coating 4 has been removed by an X-ray diffraction method. Specifically, the obtained X-ray diffraction spectrum is collated with a PDF (Powder Diffraction File). JCPDS number: 34-189 may be used to determine the presence or absence of forsterite, for example.
- JCPDS number: 34-189 may be used to determine the presence or absence of forsterite, for example.
- no forsterite peak is detected even when the surface of the steel sheet 2 from which the insulating coating 4 has been removed is analyzed by the X-ray diffraction method.
- the unidirectional electrical steel sheet 1 according to this embodiment is obtained by a manufacturing method including the following steps (A) to (D).
- the steel sheet after the powder removal step is coated with a coating liquid containing colloidal silica, and baked onto the steel sheet.
- Insulating Film Forming Step of Forming Insulating Film Each step will be described below.
- the present inventors investigated the relationship between the annealing separator applied to the steel sheet after decarburization annealing prior to finish annealing, and the amount and existence form of spinel 3 formed on the surface of the steel sheet after finish annealing. Specifically, first, a large number of primary recrystallized decarburized annealed plates were prepared. Mixtures of various Al 2 O 3 and MgO having different crystal systems (annealing separating agents) were prepared into water slurries on these decarburized and annealed plates, applied, and dried. Then, the steel sheet after the application of the annealing separator was subjected to finish annealing in dry hydrogen at a soaking temperature of 1200° C.
- the spinel 3 content was converted.
- the existence form of the spinel 3 was judged by observing the cross section in the plate thickness direction of the steel plate 2 in which the insulating film 4 was dissolved and removed and then observing the magnification at 1000 times using an optical microscope.
- a coating solution containing Al phosphate and colloidal silica as a main component is applied to the steel sheet from which the unreacted annealing separator after the final annealing has been washed away, and the steel sheet is baked at 835° C. for 30 seconds to give tension to the steel sheet.
- the insulating film 4 was formed.
- the steel sheet 2 on which the insulating coating 4 was formed was pressed against a cylinder so that the bending diameter was 20 mm, and was bent back to observe the peeling of the insulating coating 4 to evaluate the coating adhesion.
- Al 2 O 3 used as the annealing separator is composed of a mixed phase containing a ⁇ phase and an ⁇ phase, the BET specific surface area of MgO is 5.0 m 2 /g or less, and the Al 2 O 3 and MgO are When the weight ratio of MgO to the total weight of and was 5 to 50%, the spinel 3 was convex with respect to the steel plate 2, and the adhesion of the insulating film 4 was good.
- the annealing separating agent containing Al 2 O 3 and MgO is applied to the decarburized and annealed steel sheet.
- Al 2 O 3 is composed of a mixed phase containing a ⁇ phase and an ⁇ phase
- the BET specific surface area of MgO is 5.0 m 2 /g or less
- Al 2 O 3 and MgO are included.
- a decarburization annealing oxide layer containing SiO 2 is formed near the surface of the steel sheet after decarburization annealing.
- This decarburized annealing oxide layer is softened and melted in the final annealing step after the application of the annealing separator.
- the annealing separator contains Al 2 O 3 but does not contain MgO, a large part of SiO 2 generated near the surface of the steel sheet during decarburization annealing is adsorbed by Al 2 O 3 near the surface of the steel sheet.
- the formation of mullite is suppressed.
- the weight ratio of MgO to the total weight of Al 2 O 3 and MgO is less than 5%, the formation of mullite is not sufficiently suppressed.
- the ratio of the weight of MgO to the total weight of Al 2 O 3 and MgO exceeds 50%, a forsterite film is formed.
- Al 2 O 3 in the annealing separator is composed of a mixed phase containing a ⁇ phase and an ⁇ phase, SiO 2 generated near the surface of the steel sheet 2 and Al (solid solution Al) in the steel sheet 2 are formed. It is possible to effectively suppress mullite from reacting with.
- Al 2 O 3 does not include a ⁇ phase, for example, is composed of a ⁇ phase and an ⁇ phase, although a certain effect can be obtained for preventing oxides from remaining on the surface of the steel sheet 2, thermally oxidized SiO 2 Unless an intermediate layer such as a film is formed, the adhesion between the steel plate 2 and the insulating film 4 becomes insufficient, which is not preferable.
- the proportion of the ⁇ phase in Al 2 O 3 is preferably 5.0 to 50.0% in mass %. If there is a large amount of ⁇ phase, excessive hydration reaction proceeds during the preparation of the water slurry of the annealing separator, and the water contained in the hydrate of alumina is released during the finish annealing of the steel sheet coated with this water slurry. There is a concern that moisture may form an oxide.
- the proportion of the ⁇ phase in Al 2 O 3 is 50.0% by mass or less, the hydration reaction of the annealing separator during the preparation of the water slurry is suppressed, and the oxide during finish annealing of the steel sheet coated with this water slurry is suppressed.
- the BET specific surface area of MgO contained in the annealing separator is set to 5.0 m 2 /g or less. From the viewpoint of preventing the hydration reaction, the BET specific surface area of MgO is preferably 2.0 m 2 /g or less.
- Al 2 O 3 in the annealing separator preferably has a BET specific surface area of 1 to 100 m 2 /g.
- the BET specific surface area is less than 1 m 2 /g, Al 2 O 3 may be burned, which is not preferable. If the BET specific surface area of Al 2 O 3 is 1 m 2 /g or more, it is possible to further suppress the seizure of Al 2 O 3 .
- the hydration reaction proceeds in the step of preparing the water slurry of the annealing separator, and the water contained in the hydrate of alumina is released during the finish annealing, so that the steel sheet It is not preferable because it may oxidize 2.
- the BET specific surface area of Al 2 O 3 is 100 m 2 /g or less, the hydration reaction of the annealing separator during the preparation of the water slurry can be suppressed, and the oxidation of the steel sheet 2 during the finish annealing can be suppressed. ..
- the weight ratio of MgO in the annealing separator can be determined by weighing Al 2 O 3 and MgO to prepare the annealing separator when preparing the mixture of Al 2 O 3 and MgO in the water slurry.
- Al 2 O 3 containing the ⁇ -phase and ⁇ -phase as Al 2 O 3 in the preparation of the annealing separator, the Al 2 O 3 in the annealing separator, mixed phase comprising the ⁇ -phase and ⁇ -phase
- the Al 2 O 3 in the annealing separator consists of a mixed phase containing a ⁇ phase and an ⁇ phase
- the BET specific surface area of Al 2 O 3 and MgO contained in the annealing separator is a general method for evaluating the surface area of the inorganic mineral powder, and is obtained by the following method.
- the BET specific surface area of Al 2 O 3 and MgO is obtained by a method of adsorbing an inert gas such as argon on the particle surface and measuring the pressure before and after the adsorption to measure the surface area.
- the coating amount of the annealing separator is not limited, it is preferably 5 g/m 2 to 20 g/m 2 . If the coating amount is less than 5 g/m 2 , the steel sheets cannot be sufficiently covered, and seizure between the steel sheets may occur during finish annealing. When the applied amount of the annealing separator is 5 g/m 2 or more, it becomes possible to prevent seizure between the steel sheets during finish annealing. On the other hand, when the applied amount of the annealing separator is more than 20 g/m 2, the amount of water introduced between the steel sheets is large. It is feared that this moisture will be released during finish annealing and cause oxidation of the steel sheet. When the applied amount of the annealing separator is 20 g/m 2 or less, it becomes possible to suppress the oxidation of the steel sheet.
- the method for obtaining the decarburized and annealed steel sheet prior to the step of applying the annealing separator is not particularly limited.
- the molten steel adjusted to the required composition (chemical composition) is cast by an ordinary method (for example, continuous casting) to produce a slab for producing a grain-oriented electrical steel sheet.
- this slab is subjected to normal hot rolling to obtain a hot rolled steel sheet, and this hot rolled steel sheet is wound to obtain a hot rolled coil.
- the hot-rolled coil is rewound, hot-rolled sheet is annealed, and then cold-rolled once, or cold-rolled a plurality of times with intermediate annealing, to obtain the same thickness as the final product.
- a decarburized and annealed steel sheet is obtained by subjecting the steel sheet after cold rolling to decarburization and annealing.
- finish annealing is performed on the steel sheet coated with the annealing separating agent.
- the finish annealing is preferably performed at an annealing temperature (soaking temperature) of 1200° C. to 1250° C. and a soaking time of 5 to 20 hours.
- soaking temperature annealing temperature
- spinel is formed on the steel sheet. If the annealing temperature is less than 1200° C., the impurity elements in the steel sheet, such as N, are not sufficiently purified, and inclusions may be formed to cause magnetic deterioration. If the annealing temperature is 1200° C.
- the soaking temperature is higher than 1250°C, seizure between steel sheets may occur even if an annealing separator is used. When the soaking temperature is 1250° C. or lower, it becomes possible to further suppress the seizure between steel sheets. If the soaking time is less than 5 hours, the impurity elements in the steel sheet, such as N, may not be sufficiently purified, and inclusions may be formed to cause magnetic deterioration.
- the soaking time is 5 hours or more, purification can be more sufficiently performed, formation of inclusions can be suppressed, and deterioration of magnetism can be suppressed.
- the productivity is lowered, which is not preferable. If the soaking time is 20 hours or less, the productivity can be maintained.
- ⁇ Powder removal process> In the powder removing step, after the finishing annealing step is completed, excess annealing separator such as unreacted annealing separator on the surface of the steel sheet is removed by washing with water or the like. If the excess annealing separator is not sufficiently removed during the finish annealing of the steel sheet surface without performing the powder removing step, the space factor is deteriorated and the performance as the iron core is deteriorated.
- the insulating film is formed on the steel plate 2 by applying a coating solution containing colloidal silica to the steel plate 2 (intermediate steel plate having the steel plate 2 and the spinel 3 on the steel plate) after the powder removing step and baking. 4 is formed.
- the coating liquid may further contain a phosphate such as aluminum phosphate and chromic acid.
- the baking conditions are not limited, but for example, baking is performed at 835 to 870° C. for 20 to 100 seconds in an atmosphere containing at least either nitrogen 3 to 97% or hydrogen 3 to 97%.
- the baking atmosphere may contain water vapor derived from the water contained in the coating liquid, which is generated when the coating liquid is dried and baked. Therefore, the baking atmosphere is not limited to a completely dry atmosphere, that is, a system containing no water.
- the conditions in the example are one condition example adopted for confirming the feasibility and effects 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.
- Example 1 The decarburization annealed plate (plate thickness: 0.23 mm) having the chemical composition shown in Table 1-1 and having been subjected to primary recrystallization was coated with an annealing separator and dried.
- the components of the decarburized annealed plate were measured by using ICP-AES, by using the combustion-infrared absorption method for C and S, and by using the inert gas melting-thermal conductivity method for N.
- the annealing separator, and a and MgO Al 2 O 3 the ratio of the weight of MgO based on the total weight of Al 2 O 3 and MgO, and a BET specific surface area of MgO so that the values listed in Table 2 The adjusted one was used.
- Al 2 O 3 used as the annealing separator contained only the ⁇ phase and did not contain the ⁇ phase.
- No. In b4 to b6, Al 2 O 3 used as the annealing separator contained the ⁇ phase and the ⁇ phase, and did not contain the ⁇ phase.
- the steel sheet coated with the annealing separator was subjected to finish annealing at 1200° C. for 20 hours. Then, the steel sheet after the finish annealing was washed with water to wash away the unreacted annealing separator. A coating solution containing phosphate and colloidal silica is applied to the steel sheet after being washed with water, and baked at 850° C.
- the Al 2 O 3 used in the annealing separator made from a mixed phase comprising the ⁇ -phase and ⁇ -phase, BET specific surface area of MgO is not more than 5.0 m 2 / g, Al 2
- the weight ratio of MgO to the total weight of O 3 and MgO was 5 to 50%
- the spinel was convex with respect to the steel plate and the amount was 5 to 50 mg/m 2 .
- the adhesion of the insulating film was good and the iron loss was also excellent.
- No. In b5 and b6, Al 2 O 3 in the annealing separator did not include the ⁇ phase.
- Example 2 A unidirectional electrical steel sheet was manufactured under the same conditions as in Example 1. However, in this example, the ratio of the ⁇ phase in Al 2 O 3 and the coating amount of the annealing separator were also changed. A sample was taken of the obtained grain-oriented electrical steel sheet, and the amount of spinel formed between the steel sheet and the spinel was measured by the same method as in Example 1 to evaluate iron loss and coating adhesion. The results are shown in Table 3.
- a unidirectional electrical steel sheet having excellent magnetic properties and excellent adhesion between the steel sheet and the insulating film can be obtained. Therefore, it has high industrial applicability.
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Abstract
Description
しかしながら、外部酸化型酸化膜を形成するには、絶縁皮膜形成前に熱処理等を行う必要があり、生産性が低下する。
本発明者らが外部酸化型酸化膜を形成する必要のない製造方法を適用することを前提として検討した結果、鋼板と皮膜との界面の鋼板上にスピネル(MgO・Al2O3)を形成することで、フォルステライト皮膜がなく、かつ、鋼板と絶縁皮膜との間に酸化膜等の中間層がない場合でも、絶縁皮膜の密着性を向上させることができることを見出した。また、フォルステライト皮膜がなく、スピネルが存在する一方向性電磁鋼板を得る場合、仕上げ焼鈍時に用いる焼鈍分離剤を適切に選択することが重要であることを見出した。
(1)鋼板と、前記鋼板上に配された絶縁皮膜と、前記鋼板と前記絶縁皮膜との界面で前記鋼板上の一部に、前記絶縁皮膜に嵌入して存在するスピネルと、を有し、前記スピネルの量が、前記鋼板の表面の単位面積あたり、5~50mg/m2である、一方向性電磁鋼板。
(2)(1)に記載の一方向性電磁鋼板の製造方法であって、脱炭焼鈍された鋼板に、Al2O3とMgOとを含む焼鈍分離剤を塗布する焼鈍分離剤塗布工程と、前記鋼板に、仕上げ焼鈍を行う仕上げ焼鈍工程と、前記仕上げ焼鈍工程後の前記鋼板の表面の余分な焼鈍分離剤を除去する除粉工程と、前記除粉工程後の前記鋼板に、コロイダルシリカを含む塗布液を塗布し、焼き付けることで前記鋼板上に絶縁皮膜を形成する絶縁皮膜形成工程とを有し、前記Al2O3が、κ相とα相とを含む混合相からなり、前記MgOのBET比表面積が5.0m2/g以下であり、前記Al2O3と前記MgOとの合計重量に対する前記MgOの重量の割合が、5~50%である、一方向性電磁鋼板の製造方法。
(3)前記Al2O3における前記κ相の割合が、質量%で、5.0~50.0%である、(2)に記載の一方向性電磁鋼板の製造方法。
(4)前記焼鈍分離剤塗布工程における、前記焼鈍分離剤の塗布量が、5~20g/m2である、(2)または(3)に記載の一方向性電磁鋼板の製造方法。
また、本発明の一方向性電磁鋼板の製造方法によれば、磁気特性と皮膜密着性とに優れる一方向性電磁鋼板を提供できる。
図1に示されるように、本実施形態に係る一方向性電磁鋼板1は、鋼板2と、鋼板2上に形成された絶縁皮膜4と、鋼板2と絶縁皮膜4との界面の一部に、絶縁皮膜4に嵌入して形成されたスピネル3とを有している。本実施形態では、仕上げ焼鈍前にAl2O3とMgOとを含む焼鈍分離剤を塗布しており、鋼板2と絶縁皮膜4との間にはフォルステライト皮膜が形成されない。また、鋼板2と絶縁皮膜4との間の界面の一部にはスピネル3が形成されているものの、酸化膜のような中間層は形成されていない。
以下、本実施形態に係る一方向性電磁鋼板1が含む、鋼板2、スピネル3、絶縁皮膜4のそれぞれについて詳細に説明する。
鋼板2の成分は、通常の一方向性電磁鋼板に適用される範囲であれば特に限定されない。絶縁皮膜を形成した後に、一方向性電磁鋼板としての好ましい特性が得られる化学組成を有する鋼板として、例えば、C:0.085%以下、Si:0.80~7.00%、Mn:1.00%以下、Al:0.065%以下、S:0.013%以下、Cu:0~0.80%、N:0~0.012%、P:0~0.5%、Ni:0~1.0%、Sn:0~0.3%、Sb:0~0.3%を含有し、残部がFeおよび不純物からなる鋼板が例示される。
一般には、特許文献10に記載されるように、鋼板の表面上には酸化物等が残留しないことが指向される。一方で、鋼板2の表面にフォルステライト皮膜が形成されず、かつ酸化物等も残留しない場合、鋼板2表面が平滑になるので、鋼板2と絶縁皮膜4との密着性が十分に得られないという課題があった。本発明者らは、絶縁皮膜4を形成する前の、フォルステライト皮膜が形成されていない鋼板2と絶縁皮膜4との密着性を向上させる方法について種々検討を行った。その結果、絶縁皮膜4を形成する前の鋼板2の表面にスピネル3を形成することで、鋼板2と絶縁皮膜4との密着性を向上させることができることを新たに見出した。具体的には以下の通りである。
本実施形態では、このように形成されたスピネル3を「凸型スピネル」という場合がある。
本実施形態に係る一方向性電磁鋼板1では、鋼板2の表面が平滑でありかつフォルステライト皮膜が形成されていないものの、上述のように鋼板2の表面にスピネル3(凸型スピネル)が形成されることで、絶縁皮膜4の密着性を高めることができる。
皮膜密着性向上効果を得るためには、スピネル3(凸型スピネル)を、鋼板2の表面の単位面積あたり、5~50mg/m2存在させる必要がある。スピネル3(凸型スピネル)が形成されていても、含有量が5mg/m2未満である場合、皮膜密着性向上効果が十分に得られない。一方、鋼板2の表面の単位面積あたりのスピネル3(凸型スピネル)量が50mg/m2を超えると、スピネル3が鋼板2の内部側にも嵌入して形成されるようになる。この場合、鉄損が大きくなる(劣化する)。そのため、スピネル3(凸型スピネル)の量を、鋼板片面当たり5~50mg/m2とする。
スピネル3は、後述するように、脱炭焼鈍された鋼板に、MgOならびに、κ相およびα相を含むAl2O3とを含む焼鈍分離剤を塗布し、その後仕上げ焼鈍を行うことによって形成される。仕上げ焼鈍によって鋼板2と、前記鋼板2上の一部に形成されたスピネル3とを有し、前記スピネル3の含有量が、5~50mg/m2である中間鋼板が得られる。
また、この中間鋼板に、絶縁皮膜4を形成することで、本実施形態に係る一方向性電磁鋼板1が得られる。
まず、スピネル3と絶縁皮膜4を有する鋼板2を、85℃に加熱した濃度40%の水酸化ナトリウム水溶液中に20分間浸漬する。次いで、流水下でウェス(布)を用いて鋼板表面を払拭し、その後流水で十分に洗浄する。最後に乾燥機に通し、水分を乾燥させる。これらの一連の操作により、絶縁皮膜4は除去され、鋼板2と鋼板2上のスピネル3とが残存する。このスピネル3を有する鋼板2に対し、広角X線回折法により、結晶相を同定し、アルミナの存在は確認されず、スピネル3が生成していることを確認する。
アルミナの存在が確認されず、スピネル3の生成が確認された条件については、Br2/CH3OH液等による化学的溶解法により、鋼板2の表面上の残留物を採取し、この残留物が溶解した均一溶液を作製した後、ICP法によってAl2O3量を算出する。次いで、算出されたAl2O3量に、(スピネルの分子量/Al2O3分子量)を乗ずる、すなわち、「(MgO・Al2O3)/Al2O3=142.3/102=1.4」を乗ずる事で、スピネル量を求める事ができる。このスピネル量とスピネル量の算出に用いた鋼板2の面積から、鋼板2の表面の単位面積あたりのスピネル3の含有量を求めることができる。
本発明では、鋼板2にはスピネル3以外には、Al2O3成分は存在しないため、上記の方法で鋼板2の表面の単位面積あたりのスピネル3の含有量を求めることができる。
なお、アルミナの存在が確認されるのは、アルミナを主体とする焼鈍分離剤がMgOを含まない場合、または、Al2O3とMgOとの合計重量に対するMgOの重量の割合が5%未満の場合である。このような場合、焼鈍分離剤に含まれるアルミナが鋼板に焼き付くため、仕上げ焼鈍後の鋼板に対して水洗や酸洗を施しても、アルミナを除去することができず、鋼板表面にアルミナが残存する。
具体的には、スピネル3と絶縁皮膜4を有する鋼板2を、85℃に加熱した濃度40%の水酸化ナトリウム水溶液中に20分間浸漬する。次いで、流水下でウェス(布)を用いて鋼板表面を払拭し、その後流水で十分に洗浄する。最後に乾燥機に通し、水分を乾燥させる。これらの一連の操作により、絶縁皮膜4は除去され、鋼板2と鋼板2上のスピネル3とが残存する。このスピネル3を有する鋼板2から、板厚方向の断面が観察面となるように、観察試料を採取し、観察面に研磨を施す。研磨済みの試料について、光学顕微鏡を用いて、倍率1000倍程度で、画像を採取する。
観察の際、金属反射を示すのが、鋼板2であり、金属反射を示さずかつ黒色に見えるのがスピネル3である。観察された画像から、黒色に見えるスピネル3が、金属反射を示す鋼板2の外側に存在していれば、スピネル3は絶縁皮膜4に嵌入して(侵入して)形成されていると判断できる。
絶縁皮膜4は、鋼板2の上に形成される。鋼板2の表面の一部にスピネル3が形成されている場合には、その部分については、絶縁皮膜4はスピネル3の上に形成される。すなわち、絶縁皮膜4は、鋼板2およびスピネル3の上に形成される。
絶縁皮膜4は、リン酸塩とコロイダルシリカ(SiO2)とを主体とする塗布液を塗布して焼付けて形成される絶縁皮膜である。この絶縁皮膜4により、母材である鋼板2に強い面張力を付与することができる。
一方、絶縁皮膜4と鋼板2との間にSiO2からなる非晶質酸化物皮膜(不図示)が形成されていてもスピネル3による絶縁皮膜4の皮膜密着性向上効果は損なわれない。SiO2皮膜が形成される場合、SiO2皮膜は、鋼板2の上に形成されるが、スピネル3上には形成されないので、スピネル3による絶縁皮膜4の密着性の向上は損なわれず、スピネル3が形成されていない部分での鋼板2と絶縁皮膜4との密着性が向上するので、鋼板2と絶縁皮膜4との密着性がさらに向上する。
本実施形態に係る一方向性電磁鋼板1は、絶縁皮膜4が除去された鋼板2の表面についてX線回折法により分析を行っても、フォルステライトのピークは検出されない。
本実施形態に係る一方向性電磁鋼板1は、以下の(A)~(D)の工程を含む製造方法によって得られる。
(A)脱炭焼鈍された鋼板に、Al2O3とMgOとを含む焼鈍分離剤を塗布する焼鈍分離剤塗布工程
(B)前記鋼板に、仕上げ焼鈍を行う仕上げ焼鈍工程
(C)前記仕上げ焼鈍後の前記鋼板の表面の未反応の焼鈍分離剤を除去する除粉工程
(D)前記除粉工程後の前記鋼板に、コロイダルシリカを含む塗布液を塗布し、焼き付けることで前記鋼板上に絶縁皮膜を形成する絶縁皮膜形成工程
以下、各工程について説明する。
本発明者らは、仕上げ焼鈍に先立って脱炭焼鈍後の鋼板に塗布する焼鈍分離剤と、仕上げ焼鈍後の鋼板の表面に形成されるスピネル3の量および存在形態との関係を調べた。具体的には、まず、一次再結晶済みの脱炭焼鈍板を多数用意した。これらの脱炭焼鈍板に、結晶系の異なる種々のAl2O3とMgOとの混合物(焼鈍分離剤)を水スラリーに調製して、塗布し、乾燥させた。次いで、焼鈍分離剤塗布後の鋼板に、乾燥水素中で均熱温度1200℃、均熱時間20時間の仕上げ焼鈍を施した。仕上げ焼鈍後、これらの鋼板を水洗し、未反応の焼鈍分離剤を洗い流した。
このようにして調製した鋼板2について、広角X線回折法により結晶相を同定し、アルミナの存在が確認されず、スピネル3の形成が確認された条件については、Br2/CH3OH液等による化学的溶解法により、鋼板2の表面上の残留物を採取し、この残留物が溶解した均一溶液を作製した後、ICP法によってAl2O3量を算出し、Al2O3の算出に用いた鋼板2の面積を基にこれをスピネル3含有量に換算した。
また、スピネル3の存在形態は上述のように、絶縁皮膜4を溶解、除去した鋼板2の板厚方向断面を研磨した後、光学顕微鏡を用いて倍率を1000倍で観察して判定した。
焼鈍分離剤が、Al2O3と所定の量のMgOとを含むことで、鋼板上にフォルステライト皮膜が形成されず、かつ、スピネルが形成される。また、ムライトの形成が抑制される。
焼鈍分離剤において、Al2O3とMgOとの合計重量に対するMgOの重量の割合が、5%未満では、ムライトの形成が十分に抑制されない。一方、Al2O3とMgOとの合計重量に対するMgOの重量の割合が50%超では、フォルステライト皮膜が形成される。
上記効果をより確実に得る場合、Al2O3におけるκ相の割合は、質量%で5.0~50.0%であることが好ましい。κ相が多いと、焼鈍分離剤の水スラリー調製中に過度の水和反応が進行し、この水スラリーを塗布した鋼板の仕上げ焼鈍中にアルミナの水和物に含まれる水分が放出され、この水分により酸化物が形成されることが懸念される。Al2O3におけるκ相の割合が50.0質量%以下であれば、焼鈍分離剤の水スラリー調製時の水和反応が抑制され、この水スラリーを塗布した鋼板の仕上げ焼鈍中の酸化物の形成を抑制することが可能となる。また、焼鈍分離剤中のAl2O3におけるκ相が少ない場合、仕上げ焼鈍後に鋼板2の内部に、例えばムライト等の析出物が残留してしまうことが懸念される。析出物が残留すると、磁壁移動の障害となり,鉄損が劣化する可能性がある。Al2O3におけるκ相の割合が5.0質量%以上であれば、仕上げ焼鈍後の鋼板2の内部の析出物の残留を抑制することが可能である。
焼鈍分離剤に用いるAl2O3に対し、2θ=10~70°程度の範囲に渡り、X線回折チャートを採取する。そして、各回折線について面間隔を求める。次いで、求めた面間隔をJCPDSカードにおけるα相Al2O3の面間隔およびκ相Al2O3の面間隔と照合し、各結晶相の存在の有無を確認する。
仕上げ焼鈍工程では、上記焼鈍分離剤を塗布した鋼板に、仕上げ焼鈍を行う。仕上げ焼鈍は、焼鈍温度(均熱温度)を1200℃~1250℃、均熱時間を5~20時間として行うことが好ましい。この仕上げ焼鈍によって鋼板上にスピネルが形成される。
焼鈍温度が1200℃に満たないと、鋼板中の不純物元素、例えばNの純化が十分でなく、介在物が形成されて、磁性劣化を引き起こす可能性がある。焼鈍温度が1200℃以上であれば、純化がより十分に行われ、介在物の形成が抑制され、磁性劣化を抑制することが可能となる。一方、均熱温度が1250℃よりも高いと、焼鈍分離剤を使用していても鋼板同士の焼き付きが生じる可能性がある。均熱温度が1250℃以下であれば、鋼板同士の焼き付きをより一層抑制することが可能となる。
均熱時間が5時間に満たないと、鋼板中の不純物元素、例えば、Nの純化が十分でなく、介在物が形成されて、磁性劣化を引き起こす可能性がある。均熱時間が5時間以上であれば、純化がより十分に行われ、介在物の形成が抑制され、磁性劣化を抑制することが可能となる。一方、均熱時間が20時間を超えると、生産性が低下するので好ましくない。均熱時間が20時間以下であれば、生産性を維持することが可能となる。
除粉工程では、仕上げ焼鈍工程の終了後、水洗等によって鋼板表面の未反応の焼鈍分離剤等の余分な焼鈍分離剤を除去する。
除粉工程を行わず、鋼板表面の仕上げ焼鈍時に余分な焼鈍分離剤の除去が不十分な場合、占積率が悪化し、鉄芯としての性能が低下してしまう。
絶縁皮膜形成工程では、除粉工程後の鋼板2(鋼板2と鋼板上のスピネル3と有する中間鋼板)に対し、コロイダルシリカを含む塗布液を塗布し、焼き付けることで前記鋼板2上に絶縁皮膜4を形成する。
塗布液には、さらに、リン酸アルミニウムなどのリン酸塩、クロム酸を含んでもよい。焼き付け条件は限定されないが、例えば窒素3~97%、または水素3~97%、の少なくともいずれかを含有する雰囲気中において、835~870℃で20~100秒焼き付けることが例示される。なお、焼き付け雰囲気は、塗布液が含有する水分由来の、塗布液の乾燥、焼き付けの際に生じる水蒸気を含有しても良い。したがって、焼き付け雰囲気は、完全乾燥雰囲気すなわち水分を含まない系に限られない。
冷延板、脱炭焼鈍板、仕上げ焼鈍板、または、絶縁皮膜を形成した一方向性電磁鋼板に対して、必要に応じて、鉄損を低減するため、磁区制御を施してもよい。磁区制御方法は特定の方法に限定されないが、例えば、レーザー照射、電子ビーム照射、エッチング、歯車による溝形成法にて、磁区制御を施すことができる。これにより、より低鉄損の一方向性電磁鋼板が得られる。
表1-1に示す化学組成を有する、一次再結晶済みの脱炭焼鈍板(板厚:0.23mm)に、焼鈍分離剤を塗布し、乾燥させた。脱炭焼鈍板の成分は、ICP-AESを用い、CおよびSについては燃焼-赤外線吸収法を用い、Nについては不活性ガス融解-熱伝導度法を用いて測定した。焼鈍分離剤には、Al2O3とMgOとを含み、Al2O3とMgOとの合計重量に対するMgOの重量の割合、およびMgOのBET比表面積を表2に記載の値になるように調整したものを用いた。また、焼鈍分離剤に用いたAl2O3については、2θ=10~70°程度の範囲に渡り、X線回折チャートを採取した。そして、各回折線について面間隔を求め、次いで、求めた面間隔をJCPDSカードにおけるα相Al2O3の面間隔およびκ相Al2O3の面間隔と照合し、各結晶相の存在の有無を確認した。その結果、表2に示すように、No.B1~B6については、焼鈍分離剤に用いたAl2O3がκ相とα相とを含んでいた。一方、No.b1~b3では、焼鈍分離剤に用いたAl2O3がα相のみを含み、κ相を含んでいなかった。また、No.b4~b6では、焼鈍分離剤に用いたAl2O3がα相とγ相とを含み、κ相を含んでいなかった。
次に、焼鈍分離剤を塗布した鋼板に対し、1200℃で20時間の仕上げ焼鈍を行った。
続いて、仕上げ焼鈍後の鋼板を、水洗し、未反応の焼鈍分離剤を洗い流した。
水洗後の鋼板に対し、リン酸塩とコロイダルシリカとを含む塗布液を塗布し、窒素90体積%、水素10体積%、(露点+30)℃の雰囲気下で、850℃で30秒の焼付けを行って、絶縁皮膜を形成させた。
また、絶縁皮膜を形成させた鋼板(一方向性電磁鋼板)に対し、レーザを照射して磁区制御を行った。
仕上げ焼鈍後の鋼板に対し、化学組成を分析した結果、表1-2の通りであった。
また、特性として、後述の方法で鉄損および皮膜密着性を評価した。
上記サンプルを、85℃に加熱した濃度40%の水酸化ナトリウム水溶液中に20分間浸漬した。次いで、流水下でウェス(布)を用いて鋼板表面を払拭し、その後流水で十分に洗浄した。最後に乾燥機に通し、水分を乾燥させた。これらの一連の操作により、絶縁皮膜を除去した。絶縁皮膜を除去した鋼板に対し、広角X線回折法により、結晶相を確認し、スピネルの生成の有無を確認した。その後、Br2/CH3OH液等による化学的溶解法により、鋼板表面上の残留物を採取し、この残留物が溶解した均一溶液を作製した後、ICP法によってAl2O3量を算出した。算出されたAl2O3量に、(スピネルの分子量/Al2O3分子量)を乗じてスピネル量を求めた。このスピネル量とスピネル量の算出に用いたサンプルの面積から、単位面積あたりのスピネル含有量を求めた。
また、スピネルが存在している例については、スピネルの存在形態を板厚方向の断面の光学顕微鏡画像から判定した。
具体的には、絶縁皮膜を除去した鋼板から、板厚方向の断面が観察面となるように、観察試料を採取し、観察面に研磨を施した。研磨済みの試料について、光学顕微鏡を用いて、倍率1000倍程度で、画像を採取した。観察された画像から、黒色に見えるスピネルが、金属反射を示す鋼板の外側に存在していれば、絶縁皮膜に嵌入して(侵入して)形成されていると判断した。
結果を表2に示す。
製造した一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。
結果を表2に示す。
製造した一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)、曲げ戻した時の皮膜残存面積率で、絶縁皮膜の皮膜密着性を評価した。絶縁皮膜の皮膜密着性の評価は、目視で絶縁皮膜の剥離の有無を判断した。鋼板から剥離しなかった皮膜の面積率(皮膜残存面積率)が95%以上をAA、90%以上95%未満をA、50%以上90%未満をB、50%未満をCとした。A以上(AまたはAA)であれば十分な皮膜の密着性が得られたと判断した。
結果を表2に示す。なお、表2中、凸型スピネル量が「0mg/m2」とは、広角X線回折法によりスピネルの生成が確認されなかったことを示す。
これに対し、No.b5、b6では焼鈍分離剤中のAl2O3が、κ相を含んでいなかった。その結果、凸型スピネルが十分に生成されず、皮膜密着性が低かった。
また、No.b1、b4では焼鈍分離剤中のAl2O3が、κ相を含んでいなかった。また、焼鈍分離剤がMgOを含んでいなかった。これらの例では、焼鈍分離剤がMgOを含んでいないため、Al2O3が鋼板に激しく焼き付いており、仕上げ焼鈍後に水洗しても鋼板表面にAl2O3が残存した。その結果、Al2O3による凹凸の増大により皮膜密着性は良好であったものの、鉄損が劣っていた。
また、No.b2、b3では、焼鈍分離剤中のAl2O3が、κ相を含んでいなかった。これらの例では、スピネルが過剰に生成され、このスピネルは、絶縁皮膜だけでなく、鋼板にも嵌入していた。その結果、スピネルにより皮膜密着性は良好であったものの、鉄損が劣っていた。
実施例1と同様の条件で、一方向性電磁鋼板を製造した。ただし、本実施例では、Al2O3中のκ相の割合および焼鈍分離剤の塗布量も変化させた。
得られた一方向性電磁鋼板に対し、サンプルを採取し、実施例1と同じ方法で鋼板とスピネルとの間に形成されたスピネル量を測定し、鉄損および皮膜密着性を評価した。
結果を表3に示す。
2 鋼板
3 スピネル(凸型スピネル)
4 絶縁皮膜
Claims (4)
- 鋼板と、
前記鋼板上に配された絶縁皮膜と、
前記鋼板と前記絶縁皮膜との界面で前記鋼板上の一部に、前記絶縁皮膜に嵌入して存在するスピネルと、
を有し、
前記スピネルの量が、前記鋼板の表面の単位面積あたり、5~50mg/m2であることを特徴とする一方向性電磁鋼板。 - 請求項1に記載の一方向性電磁鋼板の製造方法であって、
脱炭焼鈍された鋼板に、Al2O3とMgOとを含む焼鈍分離剤を塗布する焼鈍分離剤塗布工程と、
前記鋼板に、仕上げ焼鈍を行う仕上げ焼鈍工程と、
前記仕上げ焼鈍工程後の前記鋼板の表面の余分な焼鈍分離剤を除去する除粉工程と、
前記除粉工程後の前記鋼板に、コロイダルシリカを含む塗布液を塗布し、焼き付けることで前記鋼板上に絶縁皮膜を形成する絶縁皮膜形成工程と、
を有し、
前記Al2O3が、κ相とα相とを含む混合相からなり、
前記MgOのBET比表面積が5.0m2/g以下であり、
前記Al2O3と前記MgOとの合計重量に対する前記MgOの重量の割合が、5~50%である、
ことを特徴とする一方向性電磁鋼板の製造方法。 - 前記Al2O3における前記κ相の割合が、質量%で、5.0~50.0%であることを特徴とする請求項2に記載の一方向性電磁鋼板の製造方法。
- 前記焼鈍分離剤塗布工程における、前記焼鈍分離剤の塗布量が、5~20g/m2であることを特徴とする請求項2または3に記載の一方向性電磁鋼板の製造方法。
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Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4839338A (ja) | 1971-09-27 | 1973-06-09 | ||
JPS4819050B1 (ja) | 1969-10-03 | 1973-06-11 | ||
US3785882A (en) | 1970-12-21 | 1974-01-15 | Armco Steel Corp | Cube-on-edge oriented silicon-iron having improved magnetic properties and method for making same |
JPS4996920A (ja) | 1973-01-22 | 1974-09-13 | ||
JPS563414B2 (ja) | 1976-08-13 | 1981-01-24 | ||
JPS5665983A (en) | 1979-10-15 | 1981-06-04 | Allegheny Ludlum Ind Inc | Silicon steel |
JPS5844152B2 (ja) | 1978-12-27 | 1983-10-01 | 川崎製鉄株式会社 | 下地被膜をほとんど有しない方向性珪素鋼板の製造方法 |
JPS5996278A (ja) | 1982-11-25 | 1984-06-02 | Kawasaki Steel Corp | 焼鈍分離剤 |
JPH0718457A (ja) | 1993-07-01 | 1995-01-20 | Nippon Steel Corp | 方向性珪素鋼板用焼鈍分離剤 |
JPH08134660A (ja) * | 1994-11-02 | 1996-05-28 | Nippon Steel Corp | 極めて低い鉄損を有する一方向性電磁鋼板 |
WO2002088403A1 (fr) * | 2001-04-23 | 2002-11-07 | Nippon Steel Corporation | Procede de production de tole d'acier au silicium unidirectionnel exempte de pellicule de revetement minerale inorganique |
JP4473489B2 (ja) | 2002-04-25 | 2010-06-02 | 新日本製鐵株式会社 | 一方向性珪素鋼板とその製造方法 |
WO2015064472A1 (ja) * | 2013-10-30 | 2015-05-07 | Jfeスチール株式会社 | 磁気特性および被膜密着性に優れる方向性電磁鋼板 |
JP2019005131A (ja) | 2017-06-23 | 2019-01-17 | 株式会社三共 | 遊技機 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS563414A (en) | 1979-06-22 | 1981-01-14 | Mitsubishi Electric Corp | Sound recorder/reproducer |
JPS5844152A (ja) | 1981-09-10 | 1983-03-15 | 日本設備コア株式会社 | プラスチツク製タイル |
JPS6017261A (ja) * | 1983-07-11 | 1985-01-29 | Nissan Motor Co Ltd | ペ−パライザ |
DE69218511T2 (de) * | 1991-07-10 | 1997-11-06 | Nippon Steel Corp | Kornorientiertes Siliziumstahlblech mit ausgezeichneten primären Glasfilmeigenschaften |
US7942982B2 (en) * | 2006-11-22 | 2011-05-17 | Nippon Steel Corporation | Grain-oriented electrical steel sheet excellent in coating adhesion and method of producing the same |
EP2377961B1 (en) * | 2008-12-16 | 2020-04-29 | Nippon Steel Corporation | Grain-oriented electrical steel sheet, and manufacturing method thereof |
EP3048180B2 (en) * | 2013-09-19 | 2022-01-05 | JFE Steel Corporation | Grain-oriented electrical steel sheet, and method for manufacturing same |
JP7040888B2 (ja) * | 2016-10-12 | 2022-03-23 | 日本製鉄株式会社 | 方向性電磁鋼板及び方向性電磁鋼板の張力絶縁被膜形成方法 |
-
2020
- 2020-01-16 EP EP20740801.4A patent/EP3913098A4/en active Pending
- 2020-01-16 WO PCT/JP2020/001156 patent/WO2020149328A1/ja unknown
- 2020-01-16 JP JP2020566448A patent/JP7256405B2/ja active Active
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- 2020-01-16 KR KR1020217024421A patent/KR102557225B1/ko active IP Right Grant
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- 2020-01-16 CN CN202080008991.1A patent/CN113302324B/zh active Active
- 2020-01-16 BR BR112021013601-0A patent/BR112021013601A2/pt active Search and Examination
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4819050B1 (ja) | 1969-10-03 | 1973-06-11 | ||
US3785882A (en) | 1970-12-21 | 1974-01-15 | Armco Steel Corp | Cube-on-edge oriented silicon-iron having improved magnetic properties and method for making same |
JPS4839338A (ja) | 1971-09-27 | 1973-06-09 | ||
JPS4996920A (ja) | 1973-01-22 | 1974-09-13 | ||
JPS563414B2 (ja) | 1976-08-13 | 1981-01-24 | ||
JPS5844152B2 (ja) | 1978-12-27 | 1983-10-01 | 川崎製鉄株式会社 | 下地被膜をほとんど有しない方向性珪素鋼板の製造方法 |
JPS5665983A (en) | 1979-10-15 | 1981-06-04 | Allegheny Ludlum Ind Inc | Silicon steel |
JPS5996278A (ja) | 1982-11-25 | 1984-06-02 | Kawasaki Steel Corp | 焼鈍分離剤 |
JPH0718457A (ja) | 1993-07-01 | 1995-01-20 | Nippon Steel Corp | 方向性珪素鋼板用焼鈍分離剤 |
JPH08134660A (ja) * | 1994-11-02 | 1996-05-28 | Nippon Steel Corp | 極めて低い鉄損を有する一方向性電磁鋼板 |
WO2002088403A1 (fr) * | 2001-04-23 | 2002-11-07 | Nippon Steel Corporation | Procede de production de tole d'acier au silicium unidirectionnel exempte de pellicule de revetement minerale inorganique |
JP4184809B2 (ja) | 2001-04-23 | 2008-11-19 | 新日本製鐵株式会社 | 一方向性珪素鋼板の製造方法 |
JP4473489B2 (ja) | 2002-04-25 | 2010-06-02 | 新日本製鐵株式会社 | 一方向性珪素鋼板とその製造方法 |
WO2015064472A1 (ja) * | 2013-10-30 | 2015-05-07 | Jfeスチール株式会社 | 磁気特性および被膜密着性に優れる方向性電磁鋼板 |
JP2019005131A (ja) | 2017-06-23 | 2019-01-17 | 株式会社三共 | 遊技機 |
Non-Patent Citations (2)
Title |
---|
FUJII, H ET AL.: "Glass Film Structure of Grain- Oriented Silicon Steel Using Aluminum Nitride as an Inhibitor", JOURNAL OF MATERIALS ENGINEERING AND PERFORMANCE, vol. 3, no. 2, 30 April 1994 (1994-04-30), pages 214 - 217, XP000470001 * |
See also references of EP3913098A4 |
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