EP0695812A1 - Nanokristalline Legierung mit isolierender Beschichtung, daraus hergestellter Magnetkern und Verfahren zur Herstellung einer isolierenden Beschichtung auf der nanokristallinen Legierung - Google Patents

Nanokristalline Legierung mit isolierender Beschichtung, daraus hergestellter Magnetkern und Verfahren zur Herstellung einer isolierenden Beschichtung auf der nanokristallinen Legierung Download PDF

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Publication number
EP0695812A1
EP0695812A1 EP95111776A EP95111776A EP0695812A1 EP 0695812 A1 EP0695812 A1 EP 0695812A1 EP 95111776 A EP95111776 A EP 95111776A EP 95111776 A EP95111776 A EP 95111776A EP 0695812 A1 EP0695812 A1 EP 0695812A1
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Prior art keywords
alloy
amorphous alloy
group
solution
insulating coating
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EP95111776A
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English (en)
French (fr)
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EP0695812B1 (de
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Yoshihito Yoshizawa
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Proterial Ltd
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Hitachi Metals Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0206—Manufacturing of magnetic cores by mechanical means
    • H01F41/0213—Manufacturing of magnetic circuits made from strip(s) or ribbon(s)
    • H01F41/0226—Manufacturing of magnetic circuits made from strip(s) or ribbon(s) from amorphous ribbons
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • 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
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
    • 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
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15383—Applying coatings thereon

Definitions

  • the present invention relates to nanocrystalline alloy having an insulating coating thereon, which is excellent in high-frequency characteristics and suitable for use in various magnetic parts such as transformer, choke coil, etc., and further relates to a magnetic core made of the nanocrystalline alloy and a method for forming the insulating coating on the nanocrystalline alloy.
  • a nanocrystalline alloy which contains fine crystal grains having an average grain size of 50 nm or less in an area ratio of 50% or more of the alloy structure, has been, because of its good soft magnetic properties, used for producing magnetic cores of a common-mode choke coil, a high-frequency transformer, an electrical leak alarm, pulse transformer, etc.
  • Typical examples for such a nanocrystalline alloy are disclosed in U.S. Patent No. 4,881,989 and JP-A-1-242755.
  • the nanocrystalline alloy known in the art has been generally produced by subjecting an amorphous alloy obtained by quenching a molten or vaporized alloy to a heat treatment for forming fine crystals.
  • a method for quenching a molten alloy to produce an amorphous alloy may include a single roll method, a twin roll method, a centrifugal quenching method, a rotation spinning method, an atomization method, a cavitation method, etc.
  • a method for quenching a vaporized metal may include a sputtering method, a vapor deposition method, an ion plating method, etc.
  • the nanocrystalline alloy is produced by finely crystallizing an amorphous alloy produced by the above method, and is known to have, contrary to amorphous alloys, a good heat stability as well as a high saturation magnetic flux density, a low magnetostriction, and a good soft magnetic property.
  • the nanocrystalline alloy is also known to show a little change with time in its properties and have a good temperature stability.
  • the magnetic core used in a noise filter, a pulse transformer, etc. has been made of a highly permeable material having good high-frequency characteristics such as ferrite, an amorphous alloy, etc.
  • a material low in the magnetic core loss has been used.
  • the Fe-based nanocrystalline alloy disclosed in U.S. Patent No. 4,881,989 is described to have a high permeability and a low magnetic core loss, and therefore, suitable for the use mentioned above.
  • JP-A-63-302504 discloses to apply SiO2 powder or MgO powder on a part of or complete surface of a thin alloy ribbon or to coat a thin alloy ribbon with an alcohol solution of a modified alkyl silicate added with an acid.
  • JP-A-2-297903 discloses to form a heat-resistant insulating layer of 0.5-5 ⁇ m thick by heating a coating comprising a uniform mixture of 20-90 weight % (calculated in terms of SiO2) of a silanol oligomer and 80-10 weight % of a ceramic fine particle to allow the oligomers cross-linked each other.
  • the influence of the contraction by the heat treatment is not necessary to be considered when an amorphous alloy provided with an insulating coating is produced.
  • the contraction during the heat treatment causes defective insulation due to cracking or peeling of the insulating coating or deterioration of magnetic properties due to increased internal stress. Therefore, an insulating coating free from the above problems and a method for forming such an insulating coating on a nanocrystalline alloy has been demanded to be developed. Further, an insulating coating exhibiting sufficient insulation properties even if the insulating coating is made thinner has been required in the field of electronic circuitry which requires a small-sized magnetic core.
  • an object of the present invention is to provide a nanocrystalline alloy excellent in insulating properties.
  • Another object of the present invention is to provide a magnetic core excellent in magnetic properties at high frequency, and still another object of the present invention is to provide a method for forming an insulating coating free from the conventional problems.
  • an insulating coating formed by heating a solution of at least one insulating material selected from the group consisting of aluminum silicates, lithium silicates and magnesium methylate is free from cracking and peeling during the heat treatment for crystallization of an amorphous alloy, and a nanocrystalline alloy provided with such an insulating coating is excellent in insulating properties and suitable as a material for magnetic core used at high frequency.
  • the present invention has been accomplished based on the finding.
  • a nanocrystalline alloy having on at least one surface thereof an insulating coating, the nanocrystalline alloy having a chemical composition represented by the following formula: (Fe 1-a M a ) 100-x-y-z-b A x M' y M'' z X b (by atomic %), wherein M is at least one element selected from the group consisting of Co and Ni, A is at least one element selected from the group consisting of Cu and Au, M' is at least one element selected from the group consisting of Ti, V, Zr, Nb, Mo, Hf, Ta and W, M'' is at least one element selected from the group consisting of Cr, Mn, Al, Sn, Zn, Ag, In, platinum group elements, Mg, Ca, Sr, Y, rare earth elements, N, O and S, X is at least one element selected from the group consisting of B, Si, C, Ge, Ga and P, and each of a, x, y
  • the insulating coating having an average thickness of 2 ⁇ m or less and comprising at least one insulating material selected from the group consisting of aluminum silicates, lithium silicate and magnesium oxide.
  • a magnetic core made of the nanocrystalline alloy as defined above.
  • a method for forming an insulating coating on a nanocrystalline alloy which comprises (1) rapidly quenching a molten alloy having a chemical composition represented by the following formula: (Fe 1-a M a ) 100-x-y-z-b A x M' y M'' z X b (by atomic %), wherein M is at least one element selected from the group consisting of Co and Ni, A is at least one element selected from the group consisting of Cu and Au, M' is at least one element selected from the group consisting of Ti, V, Zr, Nb, Mo, Hf, Ta and W, M'' is at least one element selected from the group consisting of Cr, Mn, Al, Sn, Zn, Ag, In, platinum group elements, Mg, Ca, Sr, Y, rare earth elements, N, O and S, X is at least one element selected from the group consisting of B, Si, C, Ge, Ga and P, and each of a,
  • the nanocrystalline alloy of the present invention which has an insulating coating on at least one surface thereof may be produce as described below.
  • an amorphous alloy is produced by rapidly quenching a molten alloy having a chemical composition represented by the following formula: (Fe 1-a M a ) 100-x-y-z-b A x M' y M'' z X b (by atomic %), wherein M is at least one element selected from the group consisting of Co and Ni, A is at least one element selected from the group consisting of Cu and Au, M' is at least one element selected from the group consisting of Ti, V, Zr, Nb, Mo, Hf, Ta and W, M'' is at least one element selected from the group consisting of Cr, Mn, Al, Sn, Zn, Ag, In, platinum group elements, Mg, Ca, Sr, Y, rare earth elements, N, O and S, X is at least one element selected from the group consisting of B, Si, C, Ge, Ga and P, and each of a, x, y, z and b respectively satisfies 0 ⁇ a ⁇
  • a chemical composition out side the above range fails to give a sufficient effect attained by the present invention due to a remarkable reduction in specific permeability or a remarkable increasing in magnetic core lose, thereby making it unable to obtain a nanocrystalline alloy of practical characteristics.
  • a solution of at least one insulating material is applied on at least one surface of the amorphous alloy thus produced.
  • the insulating material is selected from the group consisting of aluminum silicates, modified aluminum silicates, lithium silicates and magnesium methylate.
  • the solution may include oxide powder, nitride powder, etc. which is known to be used for insulating coating.
  • the concentration of the insulating material in the solution is preferably 5 to 50 % by weight.
  • the solution thus prepared may be mixed with a solution of colloidal silica.
  • the solution may be applied on an amorphous alloy after subjecting the amorphous alloy to anodizing treatment which improves the insulating properties and corrosion resistance of the resulting nanocrystalline alloy.
  • the amount of the solution being applied on the amorphous alloy is regulated so that the thickness of the resulting insulating coating may be 2 ⁇ m or less.
  • the amorphous alloy applied with the solution is then dried at a temperature of 80-350°C, preferably for 5 seconds to 10 minutes.
  • the drying may be effected by blowing the applied solution with air or another gas such as argon, nitrogen, helium, etc. maintained at 80-350°C to rapidly dry the solution. This makes the insulating coating uniform in its thickness.
  • the amorphous alloy thus dried is usually made into a form of magnetic core by winding the thin ribbon of amorphous alloy or laminating cut sheets or punched sheets of the amorphous alloy.
  • the winding or laminating step may be carried out after heat treatment when the heat-treated alloy ribbon is sufficiently flexible.
  • the heat treatment for crystallization is carried out at a temperature not lower than the crystallization temperature of the amorphous alloy, usually at 450-700°C, for 1 minute to 24 hours in an inert gas atmosphere such as nitrogen gas atmosphere, argon gas atmosphere, etc. or an oxidizing atmosphere such as air.
  • an inert gas atmosphere such as nitrogen gas atmosphere, argon gas atmosphere, etc. or an oxidizing atmosphere such as air.
  • the magnesium methylate is oxidized to provide an insulating coating comprising magnesium oxide.
  • a thin ribbon 1 of amorphous alloy which is unwound in the direction indicated by the arrow from a winding reel 2, is allowed to pass through a solution 4 stored in a vessel 3 to apply the solution 4 on both the surface of the thin ribbon 1 of amorphous alloy.
  • the thin ribbon 1 of amorphous alloy is introduced into a drying furnace 6 kept at 80- 350°C.
  • the dried thin ribbon 1 of amorphous alloy is then wound on a winding reel 7 and subjected to the subsequent heat treatment of crystallization.
  • a thin ribbon 1 of amorphous alloy which is unwound in the direction indicated by the arrow from a winding reel 2, is allowed to pass through a roll coater 8.
  • a transfer roll 10 is partially immersed in a solution 4 stored in a vessel 3 to apply the solution 4 on the lower surface of the thin ribbon 1 of amorphous alloy, which is then introduced into a drying furnace 6 kept at 80 - 350°C.
  • the dried thin ribbon 1 of amorphous alloy is then wound on a winding reel 7 and subjected to the subsequent heat treatment of crystallization.
  • a thin ribbon 1 of amorphous alloy which is unwound in the direction indicated by the arrow from a winding reel 2, is sprayed with a solution 4 from a spray 9.
  • the thin ribbon 1 of amorphous alloy is then introduced into a drying furnace 6 kept at 80-350°C.
  • the dried thin ribbon 1 of amorphous alloy is then wound on a winding reel 7 and subjected to the subsequent heat treatment of crystallization.
  • the nanocrystalline alloy produced by the method described above has preferably a thickness of 2 to 50 ⁇ m and contains fine crystals having an average grain size of 30 nm or less, preferably in an area ratio of 50 % or more.
  • the fine crystals mainly comprise bcc Fe-phase (body centered cubic lattice phase) containing Si, and may contain an ordered lattice phase or are constituted of ordered lattice. Alloying elements other than Si, i.e., B, Al, Ge, Zr, etc. may be contained as a solid solution component in the bcc Fe-phase.
  • the remaining part other than the crystal phase mainly comprises amorphous phase.
  • a nanocrystalline alloy substantially comprising only crystal phase is also embraced within the scope of the present invention.
  • a compound phase may also be formed in a part of the alloy structure.
  • the average thickness of the insulating coating is 2 ⁇ m or less, preferably 0.01 to 1 ⁇ m.
  • An average thickness of 0.5 ⁇ m or less is particularly preferred because the size of magnetic core can be reduced while maintaining its excellent insulating properties.
  • a solution of aluminum silicate (Al2O3 ⁇ SiO2) provides the surface of nanocrystalline alloy with an insulating coating having a uniform thickness and a high resistance to peeling because internal stress is hardly generated in the alloy during the crystallization process. Therefore, the insulating properties can be improved.
  • a nanocrystalline alloy having such an insulating coating exhibits a high permeability and a low magnetic core loss at low and high frequency range.
  • Li2O ⁇ SiO2 Li2O ⁇ SiO2
  • the magnetic core made by laminating or winding the nanocrystalline alloy described above is excellent in layer insulation and has little internal stress, and therefore, suitable for magnetic core used in a high-frequency range.
  • the nanocrystalline alloy has a good affinity for a resin such as an epoxy-type resin, a cut core having a high interlaminar strength can be obtained.
  • An amorphous alloy ribbon having a width of 25.4 mm and a thickness of 18 ⁇ m was produced by quenching a molten alloy of F bal. Cu 0.9 Nb 2.8 Si 15.5 B 6.2 (atomic %) by using a single roll method. After being passed through a solution containing each insulating material listed in Table 1, the amorphous alloy ribbon was dried in a hot-gas furnace kept at 200°C. The dried amorphous alloy ribbon was then wound to form a toroidal shape of 100 mm outer diameter and 80 mm inner diameter, and then heated to 570°C in a furnace at a heating rate of 1 .5°C/min and maintained there for 15 minutes to be subjected to heat treatment in a nitrogen atmosphere. The heat-treated product was cooled to room temperature to obtain each magnetic core. The most part of the alloy structure of the resulting nanocrystalline alloy was occupied with extremely fine grains comprising bcc-phase of an average grain size of about 12 nm.
  • Insulating Material ⁇ r Pc (kW/m3) R ( ⁇ ) Thickness ( ⁇ m) Invention 1 modified aluminum silicate 640 220 135 0.8 2 lithium silicate 650 220 138 0.7 3 magnesium methylate 590 240 128 0.2 4 lithium silicate 710 210 142 1.2 5 magnesium methylate 620 260 121 0.1 Comparison 6 alumina sol 410 360 27 1.1 7 alkyl silicate 490 310 35 1.2 8 colloidal silica 480 330 29 0.2 9 - 120 590 1.1 -
  • the nanocrystalline alloy having the insulating coating of the present invention had a large value of R, which means a high interlaminar insulating resistance. This results in high magnetic properties of a high ⁇ r and a low Pc.
  • An amorphous alloy ribbon having a width of 20 mm and a thickness of 18 ⁇ m was produced by quenching a molten alloy having each chemical composition shown in Table 2 by using a single roll method. After being passed through a solution dissolving each insulating material listed in Table 2, the amorphous alloy ribbon was dried in a hot-gas furnace kept at 200°C. The dried amorphous alloy ribbon was then wound to form a toroidal shape of 100 mm outer diameter and 80 mm inner diameter, and then heated to 570°C in a furnace at a heating rate of 1 . 5°C/min and maintained there for 15 minutes to be subjected to heat treatment in a nitrogen atmosphere. The heat-treated product was cooled to room temperature to obtain each magnetic core. The most part of the alloy structure of the resulting nanocrystalline alloy was occupied with extremely fine grains comprising bcc-phase of an average grain size of about 12 nm.
  • the specific permeability ( ⁇ r ) at 10 MHz, the magnetic core loss (Pc) at 500 kHz and 0.05 T, the average thickness of the insulating coating and the resistance (R) between the innermost part the surface of the magnetic core are shown in Table 2. From Table 2, the magnetic core of the present invention is found to be excellent because of its high permeability ( ⁇ r ) and low magnetic core loss (Pc).
  • An amorphous alloy ribbon having a width of 20 mm and a thickness of 12 ⁇ m was produced by quenching a molten alloy of Fe bal. Cu1Nb3Si16B 6.5 Cr 0.5 Sn 0.05 (atomic %) by using a single roll method. After being passed through a solution of lithium silicate, the amorphous alloy ribbon was dried in a hot-gas furnace kept at each temperature listed in Table 3.
  • the dried amorphous alloy ribbon having a coating of about 1 ⁇ m thick was then wound to form a toroidal shape of 60 mm outer diameter and 50 mm inner diameter, and then heated to 570°C in a furnace at a heating rate of 1 .2°C/min and maintained there for 15 minutes to be subjected to heat treatment in a nitrogen atmosphere.
  • the heat-treated product was cooled to room temperature to obtain each magnetic core.
  • the most part of the alloy structure of the resulting nanocrystalline alloy was occupied with extremely fine grains comprising bcc-phase of an average grain size of about 12 nm.
  • An amorphous alloy ribbon having a width of 25 mm and a thickness of 12 ⁇ m was produced by quenching a molten alloy of Fe bal. Nb3Ga4Si14B7 (atomic %) by using a single roll method. After being passed through a solution containing each insulating material listed in Table 4, the amorphous alloy ribbon was dried in a hot-gas furnace kept at 200°C. The dried amorphous alloy ribbon was then wound to form a toroidal shape shown in Fig. 4, and then heated to 550°C in a furnace at a heating rate of 1. 2°C/min and maintained there for 15 minutes to be subjected to heat treatment in a nitrogen atmosphere. The heat-treated product was cooled to room temperature to obtain each magnetic core.
  • each magnetic core was impregnated with an epoxy-type resin and made into a cut core by cutting after the impregnated resin was hardened.
  • the average thickness of the insulating coating, the magnetic core loss (Pc) at 20 kHz and 0.2 T, the resistance (R) between the innermost part and the surface and the appearance of the cut surface of each magnetic core are shown in Table 4.
  • An amorphous alloy ribbon having a width of 20 mm and a thickness of 15 ⁇ m was produced by quenching a molten alloy of Fe bal. Cu1Ta3Si16B6 (atomic %) by using a single roll method. After coating on the surface of the amorphous alloy a solution of each insulating material listed in Table 5 by using a roll coater, the amorphous alloy ribbon was dried in a hot-gas furnace kept at 20 °C. The dried amorphous alloy ribbon was then wound to form a toroidal shape of 35 mm outer diameter and 30 mm inner diameter, and then heated to 550°C in a furnace at a heating rate of 1 .
  • the magnetic cores of the present invention were superior to the comparative magnetic cores because of their high permeabilities, low magnetic core losses and high insulating resistances.
  • An amorphous alloy ribbon having a width of 25 mm and a thickness of 15 ⁇ m was produced by quenching a molten alloy of F bal. Cu1Zr3Si 14.5 B 6.5 (atomic %) by using a single roll method. After spraying on the surface of the amorphous alloy a solution of each insulating material listed in Table 6, the amorphous alloy ribbon was dried in a hot-gas furnace kept at 200°C. The dried amorphous alloy ribbon was then wound to form a toroidal shape of 50 mm outer diameter and 30 mm inner diameter, and then heated to 550°C in a furnace at a heating rate of 1 . 5°C/min and maintained there for 15 minutes to be subjected to heat treatment in a nitrogen atmosphere. The heat-treated product was cooled to room temperature to obtain each magnetic core. The most part of the alloy structure of the resulting nanocrystalline alloy was occupied with extremely fine grains comprising bcc-phase of an average grain size of about 12 nm.
  • the magnetic cores of the present invention were superior to the comparative magnetic cores because of their high permeabilities, low magnetic core losses and high insulating resistances.
EP19950111776 1994-08-01 1995-07-26 Nanokristalline Legierung mit isolierender Beschichtung, daraus hergestellter Magnetkern und Verfahren zur Herstellung einer isolierenden Beschichtung auf der nanokristallinen Legierung Expired - Lifetime EP0695812B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP180037/94 1994-08-01
JP18003794 1994-08-01
JP18003794A JPH0845723A (ja) 1994-08-01 1994-08-01 絶縁性に優れたナノ結晶合金薄帯およびナノ結晶合金磁心ならびにナノ結晶合金薄帯の絶縁皮膜形成方法

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EP0695812A1 true EP0695812A1 (de) 1996-02-07
EP0695812B1 EP0695812B1 (de) 2000-01-12

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JP (1) JPH0845723A (de)
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Publication number Priority date Publication date Assignee Title
JP4688458B2 (ja) * 2003-10-30 2011-05-25 日本パイオニクス株式会社 絶縁膜成膜用原料及びそれを用いた成膜方法
CN1306057C (zh) * 2004-12-24 2007-03-21 安泰科技股份有限公司 含有微量稀土元素的铁基纳米晶合金
JP2008071982A (ja) 2006-09-15 2008-03-27 Hitachi Industrial Equipment Systems Co Ltd 変圧器
CN107142429B (zh) * 2017-05-22 2019-01-18 西安工业大学 一种制备原料全部为低纯度工业合金的Fe基非晶合金及其制备方法
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63302504A (ja) 1987-06-02 1988-12-09 Hitachi Metals Ltd 磁心およびその製造方法
JPH01242755A (ja) 1988-03-23 1989-09-27 Hitachi Metals Ltd Ｆｅ基磁性合金
US4881989A (en) 1986-12-15 1989-11-21 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
EP0400550A2 (de) * 1989-05-27 1990-12-05 TDK Corporation Weichmagnetische Legierung, Herstellungsverfahren, Magnetkern, magnetischer Schirm und gepresster Magnetkern damit
JPH02297903A (ja) 1989-02-02 1990-12-10 Hitachi Metals Ltd Ｆｅ基微結晶軟磁性合金からなる巻磁心及びその製造方法
EP0585940A1 (de) * 1992-09-03 1994-03-09 Hitachi Metals, Ltd. Legierung mit ultrafeinen Kristallkörnern und hervorragender Korrosionsbeständigkeit

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4881989A (en) 1986-12-15 1989-11-21 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
JPS63302504A (ja) 1987-06-02 1988-12-09 Hitachi Metals Ltd 磁心およびその製造方法
JPH01242755A (ja) 1988-03-23 1989-09-27 Hitachi Metals Ltd Ｆｅ基磁性合金
JPH02297903A (ja) 1989-02-02 1990-12-10 Hitachi Metals Ltd Ｆｅ基微結晶軟磁性合金からなる巻磁心及びその製造方法
US5083366A (en) * 1989-02-02 1992-01-28 Hitachi Metals, Ltd. Method for making wound magnetic core
EP0400550A2 (de) * 1989-05-27 1990-12-05 TDK Corporation Weichmagnetische Legierung, Herstellungsverfahren, Magnetkern, magnetischer Schirm und gepresster Magnetkern damit
EP0585940A1 (de) * 1992-09-03 1994-03-09 Hitachi Metals, Ltd. Legierung mit ultrafeinen Kristallkörnern und hervorragender Korrosionsbeständigkeit

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043556A1 (fr) * 1999-01-19 2000-07-27 Imphy Ugine Precision Procede de traitement d'une bande mince metallique fragile et pieces magnetiques realisees a partir d'une bande en alliage nanocristallin
EP1413632A2 (de) * 1999-01-19 2004-04-28 Imphy Ugine Precision Verfahren zum Behandeln eines dünnen und zerbrechlichen Metallbandes und aus einem nanokristallinen Legierungsband hergestellte magnetische Werkstücke
EP1413632A3 (de) * 1999-01-19 2004-07-28 Imphy Ugine Precision Verfahren zum Behandeln eines dünnen und zerbrechlichen Metallbandes und aus einem nanokristallinen Legierungsband hergestellte magnetische Werkstücke
US7075402B1 (en) 1999-01-19 2006-07-11 Imphy Ugine Precision Method for treating a brittle thin metal strip and magnetic parts made from a nanocrystalline alloy strip
FR2788455A1 (fr) * 1999-01-19 2000-07-21 Imphy Ugine Precision Procede de traitement d'une bande mince metallique fragile et pieces magnetiques realisees a partir d'une bande en alliage nanocristallin
US7629870B2 (en) 1999-01-19 2009-12-08 Imphy Ugine Precision Process for the treatment of a thin brittle metal strip and magnetic components produced from a strip made of a nanocrystalline alloy
WO2006014632A2 (en) * 2004-07-22 2006-02-09 Axcelis Technologies, Inc. Improved magnet for scanning ion beams
WO2006014632A3 (en) * 2004-07-22 2006-04-20 Axcelis Tech Inc Improved magnet for scanning ion beams
CN100417740C (zh) * 2005-04-18 2008-09-10 沈明水 高频电磁波发热装置热源材料及其制造方法
CN101572154B (zh) * 2006-02-02 2012-10-24 Nec东金株式会社 非晶质软磁合金和使用这种合金的电感部件
US10984932B2 (en) 2006-02-02 2021-04-20 Tokin Corporation Amorphous soft magnetic alloy and inductance component using the same
GB2453673A (en) * 2006-04-25 2009-04-15 Vacuumschmelze Gmbh & Co Kg Magnetic core method for production thereof and earth leakage circuit breaker
GB2453673B (en) * 2006-04-25 2010-12-15 Vacuumschmelze Gmbh & Co Kg Magnet core, process for producing a magnet core and residual current device
WO2007122592A3 (de) * 2006-04-25 2008-01-10 Vacuumschmelze Gmbh & Co Kg Magnetkern, verfahren zu seiner herstellung sowie fehlerstromschutzchalter
WO2007122592A2 (de) * 2006-04-25 2007-11-01 Vacuumschmelze Gmbh & Co. Kg Magnetkern, verfahren zu seiner herstellung sowie fehlerstromschutzchalter
DE102006024358A1 (de) * 2006-05-17 2007-11-22 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Hochfeste, bei Raumtemperatur plastisch verformbare Formkörper aus Eisenlegierungen
DE102006024358B4 (de) * 2006-05-17 2013-01-03 Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. Hochfeste, bei Raumtemperatur plastisch verformbare Formkörper aus Eisenlegierungen
EP2149616A1 (de) * 2007-04-25 2010-02-03 Hitachi Metals, Ltd. Weicher und dünner magnetstreifen, verfahren zu seiner herstellung, magnetische elemente und amorpher dünner streifen
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US9099767B2 (en) 2010-01-29 2015-08-04 Johannes Binkofski Antenna core, antenna, and methods for producing an antenna core and an antenna
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