Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C24/00—Coating starting from inorganic powder
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F5/00—Compounds of magnesium
  • C01F5/02—Magnesia
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B35/00—Boron; Compounds thereof
  • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
  • C01B35/10—Compounds containing boron and oxygen
  • C01B35/12—Borates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F5/00—Compounds of magnesium
  • C01F5/02—Magnesia
  • C01F5/06—Magnesia by thermal decomposition of magnesium compounds
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
  • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
  • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
  • C21D8/1277—Modifying the physical properties of ferrous metals or ferrous alloys 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
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
  • C21D8/12—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
  • C21D8/1277—Modifying the physical properties of ferrous metals or ferrous alloys 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
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • 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
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • 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
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/42—Magnetic properties
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D2201/00—Treatment for obtaining particular effects
  • C21D2201/05—Grain orientation

Definitions

• the present invention relates to a mixed powder, MgO particles, a method for producing a grain-oriented electrical steel sheet, a method for producing MgO particles, and a method for producing a mixed powder.
• Grain-oriented electrical steel sheets are soft magnetic materials and are mainly used as core materials for transformers. Therefore, grain-oriented electrical steel sheets are required to have magnetic properties such as high magnetization properties and low iron loss. Iron loss is power loss consumed as thermal energy when an iron core is excited with an alternating magnetic field, and from the viewpoint of energy conservation, iron loss is required to be as low as possible.
• a manufacturing method including the following steps is applied to a steel slab adjusted to a predetermined composition: hot rolling, hot rolled sheet annealing, cold rolling, decarburization annealing, and finish annealing. be done.
• the steel plate wound into a coil is annealed at high temperature for a long time to integrate the crystal orientation into the Goss orientation, which has good magnetic properties (increases the degree of orientation integration).
• an annealing separator is applied to prevent the coil from seizing.
• an annealing separator containing magnesium oxide (MgO) as a main component is often used.
• MgO magnesium oxide
• SiO 2 silicon dioxide
• SiO 4 silicon dioxide
• a forsterite (Mg 2 SiO 4 )-based film (primary film) that plays the role of providing insulation. That is, by using an annealing separator containing MgO as a main component, it is possible not only to prevent seizure during final annealing but also to improve the magnetic properties of the grain-oriented electrical steel sheet.
• Patent Document 1 discloses a powder for an annealing separator containing 0.04% by mass or more and 0.30% by mass or less of boron and whose main component is magnesium oxide, in which 3-coordinated boron in the boron is A powder for an annealing separator is disclosed, characterized in that the ratio is 70% or more and 95% or less.
• Patent Document 2 is characterized in that a raw material containing one or both of magnesium hydroxide and magnesium carbonate and boron is fired, and then the tricoordinate boron ratio is adjusted by controlling the humidity of the fired product. , a method for producing a powder for an annealing separator, wherein the proportion of 3-coordinated boron in boron contained in the powder for annealing separator is 70% or more and 95% or less. A method is disclosed.
• Patent Documents 1 and 2 both state that 1) impurity purification is influenced by the film reaction behavior at high temperatures (1100°C or higher), and 2) the film reaction behavior at high temperatures is affected by the existence form of three coordinations. 3) Boron in the 4-coordination form not only does not contribute to the purification of impurities, but also invades the steel sheet during high-temperature annealing to form Fe 2 B, causing repeated bending deterioration.
• the proportion of 3-coordinated boron is defined based on the knowledge that
• Patent Documents 1 and 2 disclose that by controlling the amount of boron and the ratio of 3-coordinated boron in powder for annealing separator, poor coating appearance due to insufficient reactivity at high temperatures and impurities from the steel can be prevented. It is said that it can solve the problem of poor purification.
• magnetic properties and film properties may be improved when the boron content in MgO is increased; It was found that when the temperature is increased, too much boron penetrates into the steel sheet, which may cause coating defects. Therefore, the techniques disclosed in Patent Documents 1 and 2 cannot be said to be sufficient in improving the appearance characteristics by suppressing the formation of film defects.
• the present invention has been made in view of the above problems, and the present invention provides a mixed powder, MgO particles,
• the object of the present invention is to provide a method for producing grain-oriented electrical steel sheets, a method for producing MgO particles, and a method for producing mixed powder.
• Precipitates (inhibitors) present during secondary recrystallization suppress the growth of crystal grains other than the Goss orientation. Therefore, the slower the decomposition of the precipitate, the better.
• Tricoordinated boron is highly reactive at low temperatures and has the effect of improving coating properties and magnetic properties.
• the present inventors have found that if the proportion of tricoordinated boron is too high, the decomposition of precipitates at low temperatures is promoted, and crystal grains with orientations other than the Goss orientation tend to grow.
• the present inventors have found that by increasing the proportion of Al compounds as inhibitors with low reactivity at low temperatures, the Al compounds are maintained at low temperatures, allowing Goss-oriented crystal grains to grow even more preferentially. I found out that it is possible.
• the magnetic properties may deteriorate.
• the amount of boron is excessive, boron nitride may be generated and the magnetic properties may deteriorate.
• the amount of Al is excessive, it may not be possible to remove Al, and the magnetic properties may deteriorate due to Al.
• the present inventors found that there is an appropriate range for the amount of tricoordinated boron and the amount of Al. Furthermore, the inventors of the present invention found that the B content and particle size also have an effect on reactivity, and as a result of their extensive studies, they came up with the present invention.
• the mixed powder according to one aspect of the present invention is a mixed powder for an annealing separator containing MgO as a main ingredient, and the mixed powder contains Al and B, and the Al contained in the entire mixed powder
• the B content is 0.0007% by mass or more and 0.050% by mass or less
• the B content contained in the entire mixed powder is 0.005% by mass or more and 0.040% by mass or less
• the B is The mixed powder has an average particle diameter of 0.08 ⁇ m or more and 9.0 ⁇ m or less, and satisfies the following formula (1).
• [Al] is the Al content (mass%) in the mixed powder
• [BO 3 ] is the mixed powder. This is the content (% by mass) of the above-mentioned three-coordinated boron in the powder.
• the proportion of the tricoordinated boron in the B is preferably 5% by mass or more and less than 70% by mass.
• the mixed powder described in [1] or [2] above contains Cl: 0.0005% by mass or more and 0.0300% by mass or less, and Ti: 0.25% by mass or more and 5.00% by mass or less.
• the mixed powder according to any one of [1] to [3] above preferably contains 0.0005% by mass or more and 0.0300% by mass or less of Cl.
• the mixed powder according to any one of [1] to [4] above preferably contains 0.25% by mass or more and 5.00% by mass or less of Ti.
• the mixed powder according to any one of [1] to [5] above contains MgO particles mainly composed of MgO, B-containing particles containing B, and Al-containing particles containing Al. You may.
• the MgO particles according to another aspect of the present invention contain Al and B, the Al content is 0.0007% by mass or more and 0.0500% by mass or less, and the B content is 0.005% by mass.
• the above B contains 3-coordinated boron, has an average particle diameter of 0.08 ⁇ m or more and 9.0 ⁇ m or less, and satisfies the following formula (1). 0.06 ⁇ [Al]/[BO 3 ] ⁇ 5.00...Equation (1)
• [Al] is the Al content (mass%) in the MgO particles
• [BO 3 ] is the MgO This is the content (% by mass) of the above-mentioned 3-coordinated boron in the particles.
• the mixed powder according to any one of [1] to [6] above or the MgO particles according to [7] above is used.
• the method for producing MgO particles according to yet another aspect of the present invention includes MgO particles containing one or more selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate.
• a raw material powder containing B-containing raw material particles, B-containing raw material particles containing B, and Al-containing raw material particles containing Al is fired at a temperature of 700° C. or more and 1100° C. or less in air or nitrogen atmosphere.
• the content of tricoordinated boron relative to the mass of the raw material powder may be 0.010% by mass or more and 0.040% by mass or less.
• the method for producing MgO particles according to yet another aspect of the present invention includes one or more particles selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate containing B and Al.
• Raw material particles containing two or more types are fired at a temperature of 700° C. or more and 1100° C. or less in the air or nitrogen atmosphere.
• the content of tricoordinate boron relative to the mass of the raw material particles may be 0.010% by mass or more and 0.040% by mass or less.
• a method for producing a mixed powder according to still another aspect of the present invention includes Mg containing one or more selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate.
• a raw material powder containing B-containing raw material particles, B-containing raw material particles containing B, and Al-containing raw material particles containing Al is fired at a temperature of 700° C. or more and 1100° C. or less in air or nitrogen atmosphere.
• the content of tricoordinated boron relative to the mass of the raw material powder may be 0.010% by mass or more and 0.040% by mass or less.
• a mixed powder, MgO particles, a method for producing grain-oriented electrical steel sheets, and production of MgO particles are used to suppress the formation of coating defects due to the application of boron and to produce grain-oriented electrical steel sheets with good appearance characteristics.
• a method and a method for producing a mixed powder can be provided.
• a mixed powder according to an embodiment of the present invention is a mixed powder for an annealing separator containing MgO as a main ingredient, the mixed powder contains Al and B, and the Al content contained in the whole mixed powder is 0.0007% by mass or more and 0.050% by mass or less, the B content contained in the entire mixed powder is 0.005% by mass or more and 0.040% by mass or less, and the B contains 3-coordinated boron.
• the mixed powder has an average particle size of 0.08 ⁇ m or more and 9.0 ⁇ m or less, and satisfies the following formula (1).
• the mixed powder according to this embodiment has MgO as a main ingredient.
• the mixed powder contains, for example, 50.0% by mass or more of MgO.
• the proportion of MgO in the mixed powder is preferably 80.0% by mass or more, more preferably 90.0% by mass or more.
• the mixed powder contains MgO particles, the MgO particles contained in the mixed powder are not limited to MgO particles according to an embodiment of the present invention described below, and for example, the proportion of MgO in the mixed powder is 50.0% by mass or more. MgO particles can be used.
• Al content is 0.0007% by mass or more and 0.050% by mass or less
• the mixed powder contains Al.
• the Al content contained in the entire mixed powder is less than 0.0007% by mass, the amount of Al that fixes nitrogen decreases, and the appearance of the film deteriorates.
• the Al content contained in the entire mixed powder exceeds 0.050% by mass, the magnetic properties will deteriorate. Therefore, the Al content contained in the entire mixed powder is 0.0007% by mass or more and 0.050% by mass or less.
• the Al content contained in the entire mixed powder may be 0.003% by mass or more, 0.004% by mass or more, or 0.005% by mass or more.
• the Al content contained in the whole mixed powder may be 0.045 mass % or less, 0.040 mass % or less, or 0.030 mass % or less.
• the mixed powder includes, for example, Al-containing particles containing Al.
• the Al-containing particles contain an Al compound, and examples of the Al compound include Al 2 O 3 , AlN, Al(OH) 3 , and AlO(OH).
• the mixed powder according to this embodiment contains boron (B).
• the mixed powder includes, for example, B-containing particles containing B.
• the B- containing particles may contain at least one of pure boron and a B compound, and examples of the B compound include Na2B4O7 , borax, calcium borate, and magnesium borate. It will be done.
• the mixed powder contains 0.005% by mass or more and 0.040% by mass or less of boron (B). If the B content is less than 0.005% by mass, the structure of the coating will not be strengthened due to the lack of boron, and the coating will be destroyed when gas is released from the steel sheet, resulting in poor appearance of the grain-oriented electrical steel sheet. deteriorates. Moreover, if the B content is less than 0.005% by mass, the thickness of the coating becomes non-uniform due to a lack of boron, so that the coating tension of the grain-oriented electrical steel sheet deteriorates.
• the B content is preferably 0.008% by mass or more, more preferably 0.010% by mass or more.
• the B content in the mixed powder exceeds 0.040% by mass, the heat resistance of the internal oxidation layer will be too high, resulting in an atmosphere of gas elements such as nitrogen in the steel sheet that becomes gas at the temperature during finish annealing. If the permeation into the material is too inhibited, the gas pressure will become too high, and the film will break and the gas will be released, resulting in a deterioration in the appearance of the grain-oriented electrical steel sheet. Therefore, the B content in the mixed powder is set to 0.040% by mass or less.
• the B content is preferably 0.035% by mass or less, more preferably 0.030% by mass or less.
• the Al content and B content of the mixed powder are determined by quantitative analysis using inductively coupled plasma mass spectrometry (ICP-MS). Quantitative analysis by ICP-MS is performed by dissolving the mixed powder in a mixed acid of hydrochloric acid and nitric acid. At this time, if there is any undissolved residue, the residue is collected, dissolved in an alkaline solution, and analyzed.
• ICP-MS inductively coupled plasma mass spectrometry
• the boron contained in the mixed powder exists in the form of 3-coordinated boron (BO 3 ) and 4-coordinated boron (BO 4 ).
• 3-coordinated boron is boron with a 3-coordinated structure in which 3 oxygens are coordinated around a boron atom
• 4-coordinated boron is a boron in which 4 oxygens are coordinated around a boron atom.
• Boron has a four-coordinate structure. Boron other than 3-coordinated boron exists as 4-coordinated boron.
• 3-coordinated boron and 4-coordinated boron have different effects on coating defects and appearance characteristics. Specifically, 3-coordinated boron promotes film formation more than 4-coordinated boron while having a greater effect on the decomposition of precipitates. It has also been found that if the amount of tricoordinated boron is too large, the reactions of film formation and decomposition of precipitates occur too concentrated at low temperatures, resulting in film destruction due to gas release. Therefore, it was found that by shifting the timing of the decomposition of the precipitates, it was possible to form a good film while preventing film destruction.
• [Al]/[BO 3 ] is less than 0.06, the amount of Al that fixes nitrogen at a relatively low temperature stage during secondary recrystallization is insufficient, so that the gas release suppressing effect of the film due to BO 3 is reduced.
• the oxidation film becomes too strong and the coating is easily destroyed due to gas release at low temperatures, resulting in an uneven appearance of the oxide film on the surface of the steel sheet, deteriorating the appearance of the grain-oriented electrical steel sheet.
• [Al]/[BO 3 ] is preferably 0.08 or more, more preferably 0.15 or more.
• [Al]/[BO 3 ] is 5.00 or more, the formation of BN is small, so that a large amount of Al nitride is formed, and Al nitride is not formed until the relatively high temperature stage during secondary recrystallization. things are maintained. These nitrides are decomposed at high temperatures, and the nitrogen produced by the decomposition of the nitrides is released by destroying the coating, which has low strength due to the lack of BO 3 , thereby deteriorating the appearance of the grain-oriented electrical steel sheet.
• [Al]/[BO 3 ] is preferably 4.5 or less, more preferably 4.0 or less.
• the content of 3-coordinated boron in the mixed powder [BO 3 ] can be determined by multiplying the B content determined by ICP-MS by the proportion of 3-coordinated boron in B determined by the method described below. Desired
• the proportion of 3-coordinated boron in B is 5% by mass or more and less than 70% by mass
• the mixed powder preferably contains 3-coordinated boron in an amount of 5% by mass or more and less than 70% by mass relative to the content of B in the mixed powder.
• the proportion of 3-coordinated boron in B is more preferably 8% by mass or more.
• the proportion of 3-coordinated boron in B is 70% by mass or more, the reactivity becomes too high, the decomposition of precipitates is promoted, and crystal grains tend to grow in orientations other than the Goss orientation. There is.
• the proportion of 3-coordinated boron in B is more preferably 50% by mass or less. Note that tricoordinate boron is mainly contained in the B-containing particles described above, but may also be contained in MgO particles and Al-containing particles.
• the proportion of 3-coordinated boron in the B contained in the mixed powder is determined by the following method. Measurement was performed using NMR (Nuclear Magnetic Resonance), and in the obtained spectrum, peaks in the range of 27 ppm or less and 6 ppm or more were 3-coordinated boron, and peaks in the range of less than 6 ppm and -6 ppm or more were 4
• the coordinated boron the value obtained by dividing the integrated area of the peak of 3-coordinated boron by the total integrated area of the integrated area of the peak of 3-coordinated boron and the integrated area of the peak of 4-coordinated boron is the 3-coordinated boron of B. This is the proportion of boron.
• the Al content in the mixed powder is quantitatively analyzed by ICP-MS using the method described above.
• Cl chlorine
• Cl chlorine
• the mixed powder according to this embodiment contains 0.0005% by mass or more of Cl, since this further improves the film properties.
• the Cl content is more preferably 0.0008% by mass or more.
• the Cl content is preferably 0.0300% by mass or less.
• the Cl content is more preferably 0.0250% by mass or less.
• the total of one or more selected from the group consisting of Ca, Sr, and Ba is 0.02% by mass or more and 4.00% by mass or less
• Ca (calcium), Sr (strontium), and Ba (barium) are elements that increase reactivity with SiO 2 . Therefore, it is preferable to contain a total of 0.02% by mass or more of one or more selected from the group consisting of Ca, Sr, and Ba, since this further improves the adhesion.
• the total content of one or more selected from the group consisting of Ca, Sr, and Ba exceeds 4.00% by mass, desulfurization of the steel sheet may be caused due to its strong sulfidation tendency. .
• the total content of one or more selected from the group consisting of Ca, Sr, and Ba is 4.00% by mass or less, desulfurization can be sufficiently suppressed. Therefore, the total content of one or more selected from the group consisting of Ca, Sr, and Ba is preferably 4.00% by mass or less.
• Ca may be contained in the mixed powder as a Ca compound.
• the Ca compound include calcium sulfate, gypsum hemihydrate, calcined gypsum, and gypsum.
• Sr may be contained in the mixed powder as an Sr compound.
• Examples of the Sr compound include strontium sulfate.
• Ba may be contained in the mixed powder as a Ba compound. Examples of the Ba compound include barium sulfate.
• Cl, Sr, and Ba may be contained in the mixed powder as particles mainly containing each of them, or may be contained in the above-mentioned particles constituting the mixed powder.
• Ti 0.25% by mass or more and 5% by mass or less
• Ti titanium
• the oxygen partial pressure in the annealing atmosphere at high temperature is adjusted to about the decomposed oxygen partial pressure of TiO 2 to form a film. It is an element that helps increase the amount.
• the Ti content is more preferably 0.5% by mass or more.
• the Ti content is preferably 5% by mass or less.
• Ti content is more preferably 4% by mass or less.
• Ti can be included in the mixed powder, for example, as TiO 2 , titanate, titanium boride, titanium nitride, BaTiO 3 .
• Ti may be contained in the mixed powder as particles mainly containing each compound, or may be contained in the aforementioned particles constituting the mixed powder.
• impurities Components other than the above in the mixed powder according to this embodiment are MgO and impurities.
• impurities include Fe, Si, and the like. If the content of each impurity element is 0.5% by mass or less, or the total amount is 1.0% by mass or less, the influence on the magnetic properties or coating properties of the grain-oriented electrical steel sheet is small.
• the average particle size of the mixed powder is 0.08 ⁇ m or more and 9.0 ⁇ m or less in volume-based circular equivalent average particle size. If the average particle size of the mixed powder is less than 0.08 ⁇ m, it cannot be used as an annealing separator to prevent the steel plates from sticking to each other, resulting in incomplete film formation and deterioration of magnetic properties. Moreover, if the average particle size of the mixed powder is less than 0.08 ⁇ m, the formation of the film will be incomplete and the appearance will deteriorate. Furthermore, if the average particle size of the mixed powder is less than 0.08 ⁇ m, the coating will be incompletely formed and the coating tension will deteriorate.
• the average particle size of the mixed powder is preferably 0.2 ⁇ m or more. On the other hand, if the average particle size of the mixed powder exceeds 9.0 ⁇ m, the reactivity with the steel plate will be low, resulting in insufficient film formation.
• the average particle size of the mixed powder is preferably 7.0 ⁇ m or less, more preferably 6.0 ⁇ m or less.
• the average particle size of the mixed powder is determined by measuring the volume frequency particle size distribution using a laser diffraction particle size distribution analyzer (manufactured by HORIBA Corporation, (device name) LA-920), and calculating the average particle size in terms of circle equivalent diameter. This is the average particle size of the mixed powder.
• the refractive index is set to 1.74, and the mixed powder is subjected to ultrasonic dispersion treatment in pure water to measure the average particle size of the mixed powder.
• the mixed powder according to the present embodiment described above includes Mg-containing raw material particles containing one or more selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate, and B containing B. It is manufactured by firing a raw material powder containing containing raw material particles and Al-containing raw material particles containing Al at a temperature of 700° C. or more and 1100° C. or less in the air or nitrogen atmosphere.
• B-containing raw material particles include Mg-containing raw material particles, boron, boric acid, magnesium borate, sodium borate, borax, and the like.
• the B-containing raw material particles contain, for example, 0.01% by mass or more of B.
• the Al-containing raw material particles include Mg-containing raw material particles, Al2O3 , AlN, KAl ( SO4 ) 2.12H2O , Al(OH) 3 , AlO(OH), and the like.
• the Al-containing raw material particles contain, for example, 0.01% by mass or more of Al.
• the particle sizes of the Mg-containing raw material particles, Al-containing raw material particles, and B-containing raw material particles that constitute the raw material powder may be, for example, a particle size that provides the average particle size of the mixed powder described above, or Larger particle sizes are also possible.
• the mixed powder obtained by firing may be pulverized or classified by a known method.
• Each particle size of the Mg-containing raw material particles, the Al-containing raw material particles, and the B-containing raw material particles may be, for example, 0.08 ⁇ m or more, or 0.10 ⁇ m or more.
• each particle size of the Mg-containing raw material particles, the Al-containing raw material particles, and the B-containing raw material particles may be, for example, 15 ⁇ m or less, or 10 ⁇ m or less.
• the raw material powder may contain Cl, Ca, Sr, Ba, and Ti as appropriate. When these elements are contained in the raw material powder, it is sufficient that one particle contains one or more of these elements.
• the Al content in the raw material powder is preferably 0.0007% by mass or more and 0.050% by mass or less. If the Al content of the raw material particles is 0.0007% by mass or more and 0.050% by mass or less, the Al content of the produced mixed powder can be 0.0007% by mass or more and 0.050% by mass or less. .
• the Al content in the raw material powder may be 0.003% by mass or more, 0.004% by mass or more, or 0.005% by mass or more. Moreover, the Al content in the raw material powder may be 0.045% by mass or less, 0.040% by mass or less, or 0.030% by mass or less.
• the Al content in the raw material powder is adjusted in consideration of the amount of the component.
• Al is mainly contained in the Al-containing raw material particles described above, but may be contained in other particles constituting the raw material powder, such as Mg-containing raw material particles, B-containing raw material particles, Ti-containing particles, etc.
• the B content in the raw material powder is preferably 0.005% by mass or more and 0.040% by mass or less. If the B content of the raw material particles is 0.005% by mass or more and 0.040% by mass or less, the B content of the produced mixed powder can be 0.005% by mass or more and 0.040% by mass or less. .
• the B content is more preferably 0.006% by mass or more, and still more preferably 0.008% by mass or more. Further, the B content is more preferably 0.036% by mass or less, and even more preferably 0.032% by mass or less. However, if the raw material powder contains a component that volatilizes during firing, the B content in the raw material powder is adjusted in consideration of the amount of the component.
• B is mainly contained in the B-containing raw material particles described above, but may also be contained in other particles constituting the raw material powder, such as Mg-containing raw material particles, Al-containing raw material particles, Ti-containing particles, etc.
• the Al content and B content in the raw material powder are quantitatively analyzed by ICP-MS using the method described above.
• the content of 3-coordinated boron relative to the mass of the raw material powder is preferably 0.005% by mass or more and 0.040% by mass or less, more preferably 0.010% by mass or more and 0.030% by mass or less. . Further, the content of 3-coordinated boron relative to the B content of the raw material powder is preferably 5% or more and 70% or less. If the content of 3-coordinated boron with respect to the mass of the raw material powder or the content of 3-coordinated boron with respect to B content is within the above range, the 3-coordinated boron in the mixed powder after firing will be calculated according to the above formula (1). definitely satisfied.
• the content of 3-coordinated boron in the raw material powder [BO 3 ] is determined by multiplying the B content determined by ICP-MS by the proportion of 3-coordinated boron in B determined by the method described above. This is what is required.
• the raw material powder is fired at a temperature of 700° C. or more and 1100° C. or less in an air atmosphere or a nitrogen atmosphere. It is not preferable for the firing atmosphere to be other than air atmosphere or nitrogen atmosphere because it is economically disadvantageous. Furthermore, if the firing temperature is less than 700°C, the firing will be insufficient. Therefore, the firing temperature is set to 700°C or higher.
• the firing temperature is preferably 720°C or higher, more preferably 750°C or higher.
• the firing temperature is set to 1100°C or less.
• the firing temperature is preferably 1080°C or lower, more preferably 1040°C or lower.
• the firing time can be, for example, 5 minutes or more and 120 minutes or less. From the viewpoint of eliminating uneven firing, the firing time is preferably 8 minutes or more, more preferably 10 minutes or more. On the other hand, from the viewpoint of economy, the firing time is preferably 80 minutes or less, more preferably 60 minutes or less. Up to this point, the method for producing the mixed powder has been described.
• the raw material powder is made up of Mg-containing raw material particles and B-containing raw material particles, on the premise that the Mg source particles, B source particles, and Al source particles are different from each other.
• Mg-containing raw material particles serving as the Mg source
• the Mg-containing raw material particles serving as the Mg source may contain B and/or Al, or may contain other elements so that the Mg-containing raw material particles serve as the B source and/or Al source. good.
• the B-containing raw material particles may contain Al or other elements.
• the mixed powder according to the present embodiment described above has MgO particles, Al-containing particles, and B-containing particles containing tricoordinate boron, with MgO as the main ingredient and a B content of 0.005% by mass or more. It may be produced by mixing so that the amount is 0.040% by mass or less, the average particle size is 0.08 ⁇ m or more and 9.0 ⁇ m or less, and the above formula (1) is satisfied.
• the MgO particles according to one embodiment of the present invention contain Al and B, and have an Al content of 0.0007% by mass or more and 0.050% by mass or less, and a B content of 0.005% by mass or more and 0.05% by mass or less. 040% by mass or less, the B contains tricoordinated boron, has an average particle size of 0.08 ⁇ m or more and 9.0 ⁇ m or less, and satisfies the following formula (1).
• [Al] is the Al content (mass%) in the MgO particles
• [BO 3 ] is the MgO This is the content (% by mass) of the 3-coordinated boron in the particles.
• the above-mentioned characteristics of the MgO particles according to this embodiment are similar to those of the mixed powder described above, so a detailed description thereof will be omitted here.
• the proportion of the tricoordinated boron in B is preferably 5% by mass or more and less than 70% by mass, similarly to the mixed powder.
• the MgO particles contain 0.0005% by mass or more and 0.0300% by mass or less of Cl, similarly to the mixed powder. Moreover, it is preferable that the MgO particles contain Ti from 0.25% by mass to 5.0% by mass, similarly to the mixed powder.
• the MgO particles contain the above components, it means that the above components are contained in the MgO particles constituting the MgO powder, and it does not mean that particles other than the MgO particles are present alone.
• the MgO particles described above are manufactured by the following manufacturing method (I) or (II).
• (I) One selected from the group consisting of magnesium hydroxide (Mg(OH) 2 ), basic magnesium carbonate (mMgCO 3 .Mg(OH) 2 .nH 2 O), and magnesium carbonate (Mg(CO 3 )), or A raw material powder containing Mg-containing raw material particles containing two or more types, B-containing raw material particles containing B, and Al-containing raw material particles containing Al is heated at 700° C. or higher to 1100° C. in air or nitrogen atmosphere. Bake at the following temperature.
• Raw material particles containing one or more selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate containing B and Al are heated at 700° C. or higher at 1100° C. in air or nitrogen atmosphere. Fire at temperatures below °C. Each manufacturing method will be explained below.
• the manufacturing method of (I) includes Mg-containing raw material particles containing one or more selected from the group consisting of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate, and B-containing raw material containing B.
• This is a method for producing MgO particles by firing a raw material powder containing particles and Al-containing raw material particles containing Al at a temperature of 700° C. or more and 1100° C. or less in the air or nitrogen atmosphere. If the raw material powder contains a component that volatilizes during firing, the Al content and B content are adjusted in consideration of the amount of the component.
• This manufacturing method is basically the same as the method for manufacturing the mixed powder described above.
• oxides other than B and Al which are not dissolved or contained as impurities in the MgO particles, may be mixed and fired, which is different from the present manufacturing method and the above-mentioned method. This is different from the method for producing mixed powder.
• the raw material particles containing at least one of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate contain B and Al.
• the Al content is 0.0007% by mass or more and 0.050% by mass or less. If the Al content of the raw material particles is 0.0007% by mass or more and 0.050% by mass or less, the Al content of the manufactured MgO particles can be 0.001% by mass or more and 0.050% by mass or less. .
• the Al content of the raw material particles may be 0.003% by mass or more, 0.004% by mass or more, or 0.005% by mass or more. Further, the Al content of the raw material particles may be 0.045% by mass or less, 0.040% by mass or less, or 0.030% by mass or less.
• the B content is preferably 0.005% by mass or more and 0.040% by mass or less. If the B content of the raw material particles is 0.005% by mass or more and 0.040% by mass or less, the B content of the manufactured MgO particles can be 0.005% by mass or more and 0.040% by mass or less. .
• the B content is more preferably 0.008% by mass or more, and still more preferably 0.010% by mass or more. Further, the B content is more preferably 0.035% by mass or less, still more preferably 0.030% by mass or less.
• the content of tricoordinated boron relative to the B content in the raw material particles is preferably 5% or more and 70% or less. If the content of 3-coordinated boron relative to the B content is within the above range, the 3-coordinated boron in the MgO particles after firing under the firing conditions described below satisfies the above formula (1).
• the particle size of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate may be, for example, a particle size that provides the average particle size of the MgO particles described above, or a particle size larger than that. There may be.
• the MgO particles obtained by firing may be pulverized by a known method.
• Each particle size of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate may be, for example, 0.05 ⁇ m or more, or 0.08 ⁇ m or more.
• each particle size of magnesium hydroxide, basic magnesium carbonate, and magnesium carbonate may be, for example, 12 ⁇ m or less, or 10 ⁇ m or less.
• the raw material particles are fired at a temperature of 700°C or more and 1100°C or less in an air atmosphere or a nitrogen atmosphere.
• the firing atmosphere, firing temperature, and firing time are the same as the firing conditions for the raw material powder described above, so a detailed description thereof will be omitted here.
• a method for producing a grain-oriented electrical steel sheet according to an embodiment of the present invention is produced using the above-mentioned MgO particles or mixed powder as an annealing separator.
• the method for producing a grain-oriented electrical steel sheet according to the present embodiment includes, for example, a hot rolling step of hot rolling a steel slab to obtain a hot rolled sheet, and a hot rolled sheet annealing step of annealing the hot rolled sheet.
• a cold rolling step in which the hot rolled sheet after the hot rolled sheet annealing step is subjected to cold rolling to obtain a cold rolled sheet; a decarburization annealing step in which the cold rolled sheet is decarburized annealed;
• the manufacturing method including a finish annealing step of applying an annealing separator containing the MgO particles or mixed powder to the cold rolled sheet after the decarburization annealing step, drying it, and then performing finish annealing.
• grain-oriented electrical steel sheets can be manufactured.
• an annealing separator prepared by mixing the mixed powder according to the embodiment described above and water to form a slurry is used.
• Ti may be further mixed.
• this annealing separator grain-oriented electrical steel sheets with excellent coating appearance and coating adhesion can be produced.
• known manufacturing conditions for grain-oriented electrical steel sheets can be applied to the chemical composition of the steel slab and the conditions for each step, except for the annealing separator used.
• the annealing separator is TiO 2 when the mass of the mixed powder is 100%. It is preferable to mix at a ratio of 0.25 to 5.0% by mass in terms of Ti content.
• the conditions in the examples are examples of conditions adopted to confirm the feasibility and effects of the present invention. It is not limited to the conditions.
• the present invention can adopt various conditions as long as the purpose of the present invention is achieved without departing from the gist of the present invention.
• a grain-oriented electrical steel sheet was produced using the MgO particles shown in Table 1 or the mixed powder of MgO particles and TiO 2 particles shown in Table 2. Specifically, an aqueous slurry of an annealing separator containing the MgO particles shown in Table 1 or the mixed powder shown in Table 2 was applied to the cold rolled steel sheet after primary recrystallization annealing. The aqueous slurry was prepared by mixing MgO powder or mixed powder and water. The content of solids (MgO particles or mixed powder) in the aqueous slurry was 20% by mass. In all test numbers, the cold-rolled steel sheet coated with the aqueous slurry was baked at 300° C.
• a steel plate having a base steel plate and a glass coating containing a composite oxide such as forsterite (Mg 2 SiO 4 ) has a length in the longitudinal direction of 300 mm, a length in the width direction of 60 mm, and a plate thickness of 0.23 mm. manufactured electrical steel sheets.
• the "BO 3 ratio" shown in Table 1 indicates the ratio of 3-coordinated boron in B.
• the B content, Al content, and Cl content of the MgO particles and mixed powder were measured using inductively coupled plasma mass spectrometry (ICP-MS). Specifically, a solution of MgO particles or mixed powder dissolved in a mixed acid of hydrochloric acid and nitric acid was used. If a residue remained, it was collected, dissolved in an alkaline solution, and analyzed. Further, the proportion of 3-coordinated boron in B was determined by the following method.
• the magnetic properties (B8), appearance, and coating tension of the obtained grain-oriented electrical steel sheets were evaluated in the following manner.
• Magnetic properties The magnetic properties of each grain-oriented electrical steel sheet were evaluated using the following method. Specifically, a magnetic field of 800 A/m was applied to a sample having a length in the rolling direction of 300 mm and a width of 60 mm, and the magnetic flux density B8 was determined. When B8 was 1.92T or more, it was judged that the magnetic properties were good.
• the maximum area of coating defects is 2 mm 2 or more and 4 mm 2 or less
• C The color tone before the insulation coating is formed is uniform, and the maximum area of coating defects after the insulation coating is formed is 4 mm 2 or more and 6 mm 2 or less
• D The color tone before the insulation coating was formed was uneven, or the maximum area of coating defects after the insulation coating was formed was 6 mm 2 or more. An evaluation of A or B was judged as passing.
• Examples 16 and 29 Al was more than 0.050% by mass, and B8 of the grain-oriented electrical steel sheet was inferior.
• a grain-oriented electrical steel sheet was manufactured using a mixed powder containing MgO particles, 2 TiO particles, and at least one of B compound particles and Al compound particles at the blending ratio shown in Table 3.
• an aqueous slurry of an annealing separator containing the mixed powder shown in Table 3 was applied to the cold rolled steel sheet after primary recrystallization annealing.
• An aqueous slurry was prepared by mixing the mixed powder shown in Table 3 and water. The content of solids (mixed powder) in the aqueous slurry was 20% by mass.
• a cold rolled steel plate with an aqueous slurry applied to its surface was subjected to a baking treatment at 300° C.
• a grain-oriented electrical steel sheet with a thickness of 0.23 mm was manufactured.
• the B content, Al content, Cl content, and BO3 content of the mixed powder, as well as the proportion of 3 - coordinated boron in B ( BO3 ratio) were measured in the same manner as in Example 1. Ta.
• the magnetic properties (B8), appearance, and coating tension of the obtained grain-oriented electrical steel sheet were evaluated in the same manner as in Example 1. The results are shown in Table 4.
• Example No. 30 the average particle size of the mixed powder was too small, resulting in non-uniform film formation, and the grain-oriented electrical steel sheet was inferior in B8, appearance, and film tension.
• Example No. 31 the average particle size of the mixed powder was too large, resulting in non-uniform film formation, and the B8, appearance, and film tension of the grain-oriented electrical steel sheet were all inferior.
• Example No. 34 the B content in the mixed powder was too low, so the B8, appearance, and coating tension of the grain-oriented electrical steel sheet were inferior.
• Example No. 35 the B content in the mixed powder was excessive, and the appearance of the grain-oriented electrical steel sheet was inferior.
• the [Al]/[BO 3 ] value was outside the range of the above formula (1), and the B8 and appearance of the grain-oriented electrical steel sheets were inferior.
• the average particle size is in the range of 0.08 ⁇ m or more and 9.0 ⁇ m or less, and the Al content contained in the entire mixed powder is 0.0007 mass% or more and 0.050 mass% or less.
• the B content is 0.005% by mass or more and 0.040% by mass or less
• the [Al]/[BO 3 ] value is within the range of formula (1) above, and the magnetic properties of the grain-oriented electrical steel sheet, A grain-oriented electrical steel sheet with excellent appearance and coating tension was obtained.
• No. Samples No. 32, 33, and 40 had particularly excellent appearance characteristics because the [Al]/[BO 3 ] value was within 0.15 to 4.00.
• Example 3 The raw material powder and TiO 2 particles shown in Table 5 were mixed and fired under the conditions shown in Table 5 to produce the mixed powder shown in Table 6. A grain-oriented electrical steel sheet was manufactured in the same manner as in Example 1 using the prepared mixed powder. In addition, below, the powder obtained by firing without mixing TiO 2 particles may be referred to as MgO particles.
• the B content, Al content, Cl content, and BO 3 content of the raw material powder, MgO particles, and mixed powder, as well as the proportion of 3-coordinated boron in B (BO 3 ratio) are as in Example 1. Measured in a similar manner.
• the BO 3 content relative to the mass of the raw material powder was determined by multiplying the B content determined by ICP-MS by the proportion of 3-coordinated boron in B.
• the magnetic properties (B8), appearance, and coating tension were evaluated in the same manner as in Example 1. The results are shown in Table 6.
• Example No. 41 the B content in the obtained MgO particles was less than 0.005% by mass, and the appearance and coating tension of the grain-oriented electrical steel sheet manufactured using the MgO particles were inferior.
• Example No. 42 the B content in the obtained MgO particles was more than 0.040% by mass, and the appearance of the grain-oriented electrical steel sheet manufactured using the MgO particles was inferior.
• Example 43 and 44 the [Al]/[BO 3 ] value of the obtained MgO particles was outside the range of the above formula (1), and the B8 and appearance of the grain-oriented electrical steel sheets were inferior. No.
• the Al content contained in the entire MgO particles or mixed powder is 0.0007% by mass or more and 0.050% by mass or less, and the B content is 0.005% by mass.
• the average particle size of the MgO particles or mixed powder is 0.08 ⁇ m or more and 9.0 ⁇ m or less, and the [Al]/[BO 3 ] value of the MgO particles or mixed powder is the above (1 ), and a grain-oriented electrical steel sheet with excellent magnetic properties, appearance, and coating tension was obtained.
• Nos. 45 to 47, 49, 51, 54, 55, and 57 had particularly excellent appearance characteristics because the [Al]/[BO 3 ] value was within 0.15 to 4.00. No. In Example No.
• Example No. 53 the firing temperature was too high, so the particle size of the mixed powder became too large, resulting in inferior appearance and coating tension of the grain-oriented electrical steel sheet.
• Example 4 The raw material powders shown in Table 7 were fired under the conditions shown in Table 7 to produce mixed powders shown in Table 8.
• a grain-oriented electrical steel sheet was manufactured in the same manner as in Example 2 using the prepared mixed powder.
• the magnetic properties (B8), appearance, and coating tension of each produced grain-oriented electrical steel sheet were evaluated in the same manner as in Example 1. The results are shown in Table 8.
• the [Al]/[BO 3 ] value of the obtained mixed powder was outside the range of the above formula (1), and the B8 and appearance of the grain-oriented electrical steel sheets were inferior.
• Example No. 65 the firing temperature was too low, so the raw material powder was insufficiently fired, and MgO, the main ingredient, could not be obtained.
• Example No. 66 the firing temperature was too high, so the particle size of the mixed powder became too large, resulting in inferior appearance and coating tension of the grain-oriented electrical steel sheet.

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