US3856568A - Method for forming an insulating film on an oriented silicon steel sheet - Google Patents

Method for forming an insulating film on an oriented silicon steel sheet Download PDF

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US3856568A
US3856568A US00292715A US29271572A US3856568A US 3856568 A US3856568 A US 3856568A US 00292715 A US00292715 A US 00292715A US 29271572 A US29271572 A US 29271572A US 3856568 A US3856568 A US 3856568A
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steel sheet
percent
coating solution
film
oriented silicon
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O Tanaka
T Yamamoto
T Takata
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Nippon Steel Corp
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Nippon Steel Corp
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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
    • 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
    • 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
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching
    • 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 by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
    • C21D8/1288—Application of a tension-inducing coating
    • 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
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
    • C23C22/33—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also phosphates
    • 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
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • C23C22/74—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process for obtaining burned-in conversion coatings

Definitions

  • a method for producing anorientedsilicon steel sheet which a surface-film, which improves iron loss and magnetostriction characteristics of the steel sheet comprising the steps of applying to the surface of the oriented steel sheet a coating solution composed of 4 to 16 wt. percent of colloidal silica, 3 to 24 wt. percent of aluminum phosphate and 0.2 to 4.5 wt. percent of atleast one compound selected from the group consisting of chromic anhydride and chromate with or without the addition of 1 to 5 grams of boric acid and baking the thus applied coating solution at a temperature above 350C.
  • oriented steel sheet used here means a single oriented steel sheet of Fe-Si alloy containing up to 6 percent by weight of Si ormost commonly about 3 percentby weight of Si, having a so-called cube-onedge or a (110) [001] crystal structure as repeated by Miller index obtained by a combination of proper known rolling and heat-treatment of the steel sheet of this composition, in which the rolling direction is magnetically most easy to' magnetize.
  • Orient core Trade Mark of Nippon Steel Corporation
  • Orient core-HI'B Trade Mark of Nippon Steel Corporation
  • the surface film made on an oriented silicon steel sheet consists of a glassy film formed during the high temperature finishing annealing or a phosphate film applied onto the glassy film or directly onto the naked steel sheet having no glassy film.
  • the glassy film is formed by the reaction of magnesia, which is an annealing separating agent, or an oxide added, as required, to the magnesia and a surface oxidized layer of the steel sheet, and consists mostly of magnesium silicate.
  • magnesia which is an annealing separating agent, or an oxide added, as required, to the magnesia and a surface oxidized layer of the steel sheet, and consists mostly of magnesium silicate.
  • the phosphate film is made by applying an aqueous solution of such metallic phosphate as magnesium phosphate or aluminum phosphate to a steel sheet and baking the same.
  • the glassy film has an action effective to the improvement of the iron loss and magnetostriction characteristics.
  • the formation of this film is so easily influenced by the characteristics of magnesia, the state of the surface oxidized layer of the steel sheet, the annealingatmosphere and temperature conditions that it is difficult in fact to obtain a uniform thickness 2 4 and characteristics. Therefore, with only the glassy film, it is insufficient to utilize the effect of the surface film.
  • the phosphate film is low in the effect of the surface film and may even occasionally deteriorate the characteristics to be lower than in case the surface film is made of the glassy film only.
  • An object of the present invention is to provide an oriented electromagnetic steel sheet, on which is formed a surface film serving to improve the iron loss and magneto-striction characteristics.
  • Another object of the present invention is to provide an oriented electromagnetic steel 'sheet, on which is formed a surface film having good adhesive properties.
  • a further object of the present invention is to obtain a uniform surface filmon the above-mentioned steel sheet.
  • the accompanying drawing is a graph showing the difference in the effect on the iron loss between the coating of the present invention and .a conventional magnesium phosphate coating applied to bare oriented steel samples after having removed the surface film formed on the silicon steel sheet products respectively.
  • a surface film formed by applying and baking'a coating solution having colloidal silica as a main component, aluminum phosphate and at least one compound selected from the group consisting of chromic anhydride and chromates as a binder in the fundamental composition has a great effect on the improvement. of the iron loss and magnetostriction characteristics of an oriented silicon steel sheet.
  • An aqueous dispersion of supermicro-granular (for example, of a granule diameter of 10 to 20 mp.) colloidal silica performs a film formation. When the aqueous solution is applied onto a steel sheet and isbaked, a film can be formed.
  • this film has a disadvantage that it is low in the adhesion to the steel sheet. If a mixed aqueous solution of aluminum phosphate and one or more of'chromic anhydride and chromates is added to this aqueous dispersion of colloidal silica, the adhesion of the film can be improved. This is thought to be attributable to the fact that the above-mentioned mixture acts as a binder. Even with aluminum phosphate alone as a binder, the adhesion may be improved but, when the film is long exposed to a wet atmosphere, there occurs a phenomenon that the silica lamina is isolated. In order to prevent this phenomenon, it is effective to add one or more of chromic anhydride and chromates to the solution.
  • this surface film has not only the abovementioned features but also the following features for the oriented silicon steel sheet. Even when thickly applied to, it presents aa beautiful appearance and the adhesion is not impaired thereby. Therefore, a high interlayer resistance and voltage resistance can be easily obtained.
  • the film is also so flat and smooth that, even if it is thickly applied, a practically sufficient space factor can be obtained. Further, the film is so compact that it is high in the heat-proofness, atmosphere-proofness and anticorrosion.
  • the properties and mixing rates of component solutions of the coating solution to be used in the present invention are as follows.
  • Supermicrogranular colloidal silica which is dispersed in water and is a main component of the coating solution is required to obtain a sta ble mutual solubility with an aqueous solution of a phosphate, chromic acid or a chromate as a binder.
  • commercial Snowtex (Trade Mark of Nissan Chemical Industries, Ltd.) (of an SiO content of 20 percent, hydrogen ion concentration (pH) of 3.0 to 4.0 and specific gravity of 1.15 at 20C.) renders a suitable example for the present invention.
  • Aluminum phosphate to be used as a binder may be nearly of a composition of aluminum biphosphate, in which a mixing ratio of A1 0 and H PO is about 0.16 by mols and the proper pH is about 0.9 (about 1.9 as corrected by the concentration) in an aqueous solution of 50 percent. It is needless to say that the present invention is not limited to the above-mentioned values. However, according to experiences, when the pH is low, the solution bubbles and its applicability is reduced. In order to obtain the above-mentioned pH value, the said mol ratio is suitable for the preparation and there is further an advantage that a commercial product can be utilized.
  • the proper mixing ratios of components of the coating solution of the present invention are as follows: 20 to 80 parts by volume of a 50 percent aqueous solution of aluminum phosphate are added to 100 parts by volume of a 20 percent aqueous dispersion of colloidal silica.
  • This mixture corresponds to a coating solution composed of to 16 percent by weight of colloidal silica and 9 to 24 percent by weight of aluminum phosphate (as calculated as aluminum biphosphate here and hereinafter).
  • the aqueous solution of aluminum phosphate is less than parts by volume, there is shown a phenomenon that, after the baking, the adhesion of the above described silica lamina becomes insufficient and,
  • Chromic acid is of chromic anhydride powder.
  • the addition of 1 gram of chromic anhydride powder to cc. of an aqueous dispersion of colloidal silica can present the above described isolation of the silica lamina which is to be caused in the case of adding no chromic anhydride powder.
  • the proper range of the addition of chromic anhydride powder is 3 to 9 grams.
  • more than 5 parts by volume of a 25 percent aqueous solution of magnesium chromate are to be added to 100 parts by volume of colloidal silica. Then, the above-mentioned isolation of the silica lamina may be prevented.
  • the preferable range of the addition of chromate is 10 to 30 parts by volume.
  • the coating solution of the above-mentioned composition corresponds to an aqueous solution of about 8 to 16 percent by weight of colloidalsilica, 7 to 24 percent by weight of aluminum phosphate and 0.4 to 4.5 percent by weight of chromic anhydride or magnesium chromate. Further, as required, in case a thus coated steel sheet is likely to stick during the heat-treatment, for instance, in case the heat-treatment is carried out at a temperature above 800C, it will be effective to add boric acid or supermicro-granular silica.
  • boric acid or 0.25 to 2 grams of such supermicrogranular silica as, for example, commercial Nipsil VN 3 (Trade Mark of Nippon Silica Industrial Co., Ltd.) (of 93 to 94% SiO a granule diameter less than 10 p. and a pH (at 4 percent) of 5.8 to 6.8) to 100 cc. of an aqueous dispersion of colloidal silica.
  • Nipsil VN 3 Trade Mark of Nippon Silica Industrial Co., Ltd.
  • boric acid or supermicrogranular silica is carried out as follows:
  • the thus prepared solution is of a concentration of about 23 to 28 B.
  • the thus prepared solution is of a concentration of about 26 to 31 B.
  • the coating solution of the abovementioned composition is used after adjusted to be of a concentration proper for the objective film deposition amount. That is to say, it is used in the state of the original solution so as to contain 4 to 16 percent by weight of colloidal silica, 3 to 24 percent by weight of aluminum phosphate and 0.2 to 4.5 percent by weight of one or more of chromic anhydride and chromates or as diluted with water.
  • the coating solution of the present invention is uniformly applied onto the surface of the abovementioned oriented silicon steel sheet by dipping or spraying and thereafter is pressed with pressing rolls, or coated by any known method.
  • the coating solution of the present invention can be applied to an oriented silicon steel sheet, irrespective of the surface ofthe oriented silicon steel sheet being covered with a glassy film or with a phosphate film or both films or being bare without covered by them.
  • the coating solution of the present invention is baked after it has been applied to the surface of a steel sheet as above-mentioned.
  • a favorable surface film can be obtained, when it is heated to a temperature above 350+C., preferably a temperature between 400to 900C.
  • the baking temperature range is so wide as above-mentioned.
  • the lower limit of the baking temperature is set at 350C, because, if the coating temperature is below this limit, the reaction of the coating solution is insufficient and the hygroscopicity remains in the formed surface film.
  • the baking temperature may be raised up to a relatively high one, but practically the temperature above 900C. is not economical, and it is even feared that at such a high temperature above 900C. the characteristics of the surface film will be deteriorated depending upon the atmosphere and treating time. Thus, the baking temperature above 900C. is not desirable.
  • the atmosphere at the time of baking may be of air, nitrogen or a mixture of nitrogen and hydrogen.
  • the glassy film on an oriented silicon steel sheet is used to be formed by a high temperature finishing annealing. Then, the excess annealing separating agent is removed by water-washing or light pickling to leave the glassy film on the surface of the steel sheet. Or, for the purpose of improving the punchability, the glassy film may be also'removed by pickling. Then, a so-called heat-flattening is made to remove a coil bent of the steel sheet and to flatten the steel sheet. This heat-treatment is carried out at 800 to 900C. for not more than about 3 minutes.
  • This condition corresponds to the high temperature side of the above-mentioned baking condition. Therefore, if the coating solution is applied before the heat-flattening, the heat-flattening and baking are able to be simultaneously carried out. Further, as in such case, the interlayer resistance and voltage resistance are often impaired by flaws caused by builds-up on hearth rolls, the coating solution may be again applied and baked at, a low temperature in order to remedy the above-mentioned defect. Or, it is also possible to apply the coating solution and baking the same at a low temperature of 400 to 500C. after the heat-flattening.
  • EXAMPLE 1 Samples taken adjacently to one another from the same commercial coil of an oriented silicon steel sheet of a thickness of 0.30 mm. were treated with a mixed acid of sulfuric acid and hydrofluoric acid to remove the surface films an'd were then continuously annealed at 800C. in hydrogen for 3 minutes to remove stains. Thus,'the samples for the test have been prepared. To these samples there were applied a phosphate coating solution of magnesium phosphate and a coating solution of a composition of cc of a 20 percent aqueous dispersion of colloidal silica, 60 cc.
  • the Figure shows the results of the measurements of iron losses /50 and W 17/50 before and after forming films of respective coatings.
  • the reduction in iron loss obtained by the coating solution of the present invention is very large.
  • Table 1 indicates the results of the measurements of the magnetostriction characteristics.
  • the sample by the coating solution of the present invention is low in the magnetostriction and is also low in the deterioration to be caused by the compressive force.
  • Example 2 Samples taken adjacently to one another from the same coil of an oriented silicon steel sheet of a thickness of 0.30 mm., as finished annealed at a high temperature, were subjected to water-washing and light pickling to remove an annealing separating agent remained on the surfaces of the samples and to leave the glassy films and were then annealed to remove coil bents and strains. Thus, the samples for the test were prepared. To these samples covered with the glassy films there were applied a phosphate coating solution of magnesium phosphate and a coating solution of 100 cc. of a percent aqueous dispersion of colloidal silica,'60 cc.
  • Example 2 of a 50 percent aqueous solution of aluminum phosphate, 6 grams of chrornic anhydride and 0.75 gram of supermicrogranular silica of the present invention respectively in the same manner as in Example 1 and were thereafter baked at 850C. for 10 seconds in air in a continuous oven.
  • Table 2 shows the results measured in the same manner as in Example 1 before applying the coating and after applying and baking it. The effect of the surface filmby the coating solution of the present invention is large.
  • Table 3 there are shown characteristics of the surface film samples by the coating solution of the present invention after subjected to a strain-removing annealing at 800C. for 4 hours in a dry atmosphere of 10% H and N The effect of the surface film is not lost even by the heat-treatment of a long time.
  • Table 4 shows the results of measuring the coating deposition, interlayer resistance and-space factor of' these surface films.
  • the surface film of the present invention is high in the interlayer resistance and is very small particularly in the reduction in resistance to be caused by the annealing in a reducing atmosphere. Though it is high in the coating deposition, it keeps a high space factor.
  • EXAMPLE 3 1 Samples were prepared-in the same manner as in Example 2. A coating solution of a composition of 100 cc. of a 20 percent aqueous solution of colloidal silica, 60 cc. ofa 50 percent aqueous solution of aluminum phosphate, cc. of a 25 percent aqueous solution of magnesium chromate and 0.75 gram of supermicrogranular silica of the present invention was applied to these samples having glassy films andwas baked at about 450C. for 10 seconds in an open oven. These samples were further continuously annealed to remove strains at 810C. for 2 minutes in a nitrogen atmosphere.
  • Table 5 shows the results measured in the same manher as in Example 1 before and after the strainremoving annealing.
  • the improvements of the iron loss and magnetostriction characteristics after the annealing are large, showing the better characteristics than in the case of the glassy film only mentioned also in the same table. This shows that, even when the coating solution of the present invention is baked at a low temperature, a sufficient effect of the surface film can be obtained by a subsequent annealing at a high temperature.
  • EXAMPLE 4 After the treatment in Example 2, a coating solution of 100 cc.'of a 20 percent aqueous dispersion of colloidal silica, 60 cc. of a 50 percent aqueous solution of aluminum phosphate and 15 cc. of a percent aque 1 B7 .0 l .9 1 1 .1 50.0 I 33 .3 3 .7
  • the original solution was of about 25 Be
  • water to be of about 15 Be was applied to the steel sheet and was baked at 400C. for 10 seconds in an open oven.
  • the obtained surface film was flat, smooth and uniform.
  • the coating solution of the present invention can be used also for improving the interlayer resistance and voltage resistance and further for recoating for the purpose of securing the insulation of the part, after a protrusion thereof has been removed by shearing or slitting.
  • a method for forming an insulating film on an oriented silicon steel sheet comprising the steps of applying to the oriented silicon steel sheet a' coating solution composed of 4 to 16 wt. percent of colloidal silica, 3 to 24 wt. percent of aluminum phosphate, calculated as aluminum biphosphate, and 0.2 to 4.5 wt. percent of at least one compound selected from the group consisting of chromic anhydride and chromate and baking the thus applied coating solution at a temperature above 2.
  • the method according to claim 1 in which boric acid is added to the coating solution in an amount of 1 to 5 grams per cc. of a water dispersion of colloidal magnetostriction characteristic of the steel sheet, comprising the steps of forming a glassy film.
  • a coating solution composed of 4 to 16 wt. percent of colloidal silica; 3 to 24 wt. percent of aluminum phosphate, calculated as aluminum biphosphate, and 0.2 to 4.5 wt. percent of at least one compound selected from the group consisting of chromic anhydride and chromate. baking the thus applied coating solution at a temperature above 350C and then subjecting the magneto-striction characteristics of the steel sheet, ac

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US00292715A 1971-09-27 1972-09-27 Method for forming an insulating film on an oriented silicon steel sheet Expired - Lifetime US3856568A (en)

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JP7523371A JPS5328375B2 (pt) 1971-09-27 1971-09-27

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JP (1) JPS5328375B2 (pt)
BE (1) BE789262A (pt)
BR (1) BR7206706D0 (pt)
CA (1) CA986793A (pt)
DE (1) DE2247269C3 (pt)
FR (1) FR2154625B1 (pt)
GB (1) GB1411094A (pt)
IT (1) IT965500B (pt)
SE (1) SE379799B (pt)

Cited By (46)

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US3985583A (en) * 1973-11-17 1976-10-12 Kawasaki Steel Corporation Method for forming an insulating coating on an oriented silicon steel sheet
EP0008385A1 (en) * 1978-07-26 1980-03-05 Nippon Steel Corporation Grain-oriented electromagnetic steel sheet and method for its production
US4238534A (en) * 1975-08-22 1980-12-09 Kawasaki Steel Corporation Method for forming a heat-resistant coating on an oriented silicon steel sheet
EP0033878A2 (en) * 1980-01-25 1981-08-19 Nippon Steel Corporation Method for treating an electromagnetic steel sheet by laser-beam irradiation
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US4552596A (en) * 1978-07-26 1985-11-12 Nippon Steel Corporation Grain-oriented electromagnetic steel sheet with improved watt loss
US5129965A (en) * 1990-07-20 1992-07-14 Nippon Steel Corporation Method of producing grain oriented silicon steel sheets each having a low watt loss and a mirror surface
EP0565029A1 (en) * 1992-04-07 1993-10-13 Nippon Steel Corporation Grain oriented silicon steel sheet having low core loss and method of manufacturing same
EP0577124A2 (en) * 1992-07-02 1994-01-05 Nippon Steel Corporation Grain oriented electrical steel sheet having high magnetic flux density and ultra low iron loss and process for producing the same
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US20090101248A1 (en) * 2004-11-30 2009-04-23 Jfe Steel Corporation Grain-Oriented Electrical Steel Sheet and Process for Producing the Same
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WO2014121853A1 (en) 2013-02-08 2014-08-14 Thyssenkrupp Electrical Steel Gmbh Solution for forming insulation coating and grain-oriented electrical steel sheet
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KR20180053353A (ko) * 2015-09-25 2018-05-21 제이에프이 스틸 가부시키가이샤 방향성 전자 강판 및 그의 제조 방법
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FR2154625B1 (pt) 1975-01-03
JPS5328375B2 (pt) 1978-08-14
IT965500B (it) 1974-01-31
CA986793A (en) 1976-04-06
JPS4839338A (pt) 1973-06-09
DE2247269B2 (de) 1977-09-29
FR2154625A1 (pt) 1973-05-11
DE2247269A1 (de) 1973-04-05
DE2247269C3 (de) 1981-05-14
SE379799B (pt) 1975-10-20
GB1411094A (en) 1975-10-22
BE789262A (fr) 1973-01-15
BR7206706D0 (pt) 1973-08-21

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