EP3050977A1 - Verfahren zur herstellung einer eisenbasierten nanokristallinen legierung und verfahren zur herstellung eines magnetischen kerns für die eisenbasierte nanokristalline legierung - Google Patents

Verfahren zur herstellung einer eisenbasierten nanokristallinen legierung und verfahren zur herstellung eines magnetischen kerns für die eisenbasierte nanokristalline legierung Download PDF

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EP3050977A1
EP3050977A1 EP14849656.5A EP14849656A EP3050977A1 EP 3050977 A1 EP3050977 A1 EP 3050977A1 EP 14849656 A EP14849656 A EP 14849656A EP 3050977 A1 EP3050977 A1 EP 3050977A1
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Prior art keywords
temperature
magnetic field
nano
magnetic
heat treatment
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French (fr)
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EP3050977A4 (de
EP3050977B1 (de
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Hiroki Yamamoto
Nakao Moritsugu
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Proterial Ltd
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Hitachi Metals Ltd
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    • 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
    • C21D6/00—Heat treatment of ferrous alloys
    • 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
    • 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
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • 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
    • 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
    • C21D1/34—Methods of heating
    • 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
    • C21D2201/03—Amorphous or microcrystalline structure
    • 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

Definitions

  • the present invention relates to a method for producing an Fe-based nano-crystal alloy and a method for producing a magnetic core formed of an Fe-based nano-crystal alloy in a wound or stacked state.
  • An Fe-based nano-crystal alloy has beautiful soft magnetic characteristics that include both of a high saturation magnetic flux density and a high specific magnetic permeability ⁇ , and therefore is used for a magnetic core of a common mode choke coil, a high frequency transformer and the like.
  • a representative composition system of such an Fe-based nano-crystal alloy is an Fe-Cu-Nb-Si-B system described in Patent Document 1.
  • An Fe-based nano-crystal alloy is produced as follows.
  • a liquid-phase alloy heated to a temperature higher than, or equal to, a melting point thereof is rapidly solidified to obtain an amorphous alloy, and the amorphous alloy is heat-treated to be formed into nano-crystals.
  • a single roll method which provides a high productivity, is used.
  • An Fe-based nano-crystal alloy has the magnetic characteristics thereof, such as the specific magnetic permeability ⁇ , the squareness ratio and the like, changed in accordance with the temperature profile or the direction in which the magnetic field is applied, both at the time of heat treatment.
  • Patent Document 2 proposes performing heat treatment while applying a magnetic field in a width direction of a ribbon (height direction of a magnetic core) in order to obtain an Fe-based nano-crystal alloy having an initial specific magnetic permeability of 70,000 or greater and a squareness ratio of 30% or less.
  • Patent Document 2 describes various specific patterns of heat treatment, which may be roughly classified as follows: a pattern in which the ribbon is kept for a certain duration at the highest temperature reached during the heat treatment, while the magnetic field is applied; a pattern in which the ribbon is kept at a certain temperature for a certain duration during a procedure including a temperature-increasing process, when the ribbon is at the highest temperature reached and a cooling process, while the magnetic field is applied; and a pattern in which the ribbon is kept at a certain temperature for a certain duration during a procedure including when the ribbon is at highest temperature reached and a cooling process, while the magnetic field is applied.
  • Patent Document 2 The heat treatment method disclosed in Patent Document 2 is considered to be effective as a method for decreasing the squareness ratio.
  • a high frequency band at or around 100 kHz tends to be used more for a common mode choke or the like.
  • a nano-crystal alloy having a high specific magnetic permeability ⁇ in the high frequency band is desired.
  • the present inventors performed various studies in order to obtain a high specific magnetic permeability ⁇ in a high frequency band at or around 100 kHz, and as a result, have recognized that it is occasionally difficult to obtain a high specific magnetic permeability ⁇ in the high frequency band by the heat treatment patterns described in Patent Documents 1 and 2.
  • the present invention made in light of the above situation has an object of providing a method for producing an Fe-based nano-crystal alloy and a method for producing an Fe-based nano-crystal alloy magnetic core, both easily providing a high specific magnetic permeability ⁇ at or around a high frequency of 100 kHz.
  • the present inventors have found that a high specific magnetic permeability ⁇ in a high frequency band of, for example, 100 kHz is obtained by applying a magnetic field in a specific temperature range during a temperature-increasing period while an Fe-based amorphous alloy is nano-crystallized by heat treatment.
  • a method for producing an Fe-based nano-crystal alloy in an embodiment according to the present invention includes a heat treatment step of heating a nano-crystallizable Fe-based amorphous alloy ribbon to a crystallization temperature region and cooling the nano-crystallizable Fe-based amorphous alloy ribbon.
  • a magnetic field is applied in a width direction of the alloy ribbon in a temperature range during a temperature-increasing period, the temperature range including at least a part of a temperature range from a temperature lower by 50°C than a crystallization start temperature to a temperature higher by 20°C than the crystallization start temperature and not exceeding a temperature higher by 50°C than the crystallization start temperature, the crystallization start temperature being defined by a differential scanning calorimeter.
  • the magnetic field is applied selectively in the temperature range during the temperature-increasing period.
  • the magnetic field is applied at a strength of 50 kA/m or greater and 300 kA/m or less in the width direction of the alloy ribbon.
  • the magnetic field is not applied when a highest temperature was reached in the heat treatment step.
  • a method for producing an Fe-based nano-crystal alloy ribbon includes a step of preparing a nano-crystallizable Fe-based amorphous alloy ribbon, a step of heating the nano-crystallizable Fe-based amorphous alloy ribbon to a crystallization temperature region and cooling the nano-crystallizable Fe-based amorphous alloy ribbon, and a step of applying a magnetic field to the Fe-based amorphous alloy ribbon in the heat treatment step.
  • a magnetic field of a predetermined strength (e.g., 50 kA/m) or greater is applied in a width direction of the alloy ribbon in at least a part of a temperature range during a temperature-increasing period in the heat treatment step, the temperature range being from a temperature lower by 50°C than a crystallization start temperature, indicated by a differential scanning calorimeter, to a temperature higher by 20°C than the crystallization start temperature, and the magnetic field of the predetermined strength or greater is not applied in a part of the temperature-increasing period.
  • a predetermined strength e.g., 50 kA/m
  • the magnetic field of the predetermined strength or greater is not applied in a temperature-increasing period higher than a temperature higher by 50°C than the crystallization start temperature. It is not necessary to apply the magnetic field of the predetermined strength or greater in a temperature-increasing period lower than a temperature lower by 50°C than the crystallization start temperature.
  • a method for producing an Fe-based nano-crystal alloy magnetic core in an embodiment according to the present invention includes a heat treatment step of heating a nano-crystallizable Fe-based amorphous alloy ribbon to a crystallization temperature region and cooling the nano-crystallizable Fe-based amorphous alloy ribbon after the nano-crystallizable Fe-based amorphous alloy ribbon is wound or stacked.
  • a magnetic core including an Fe-based nano-crystal alloy ribbon in a wound or stacked state is produced.
  • a magnetic field is applied in a height direction of the magnetic core in a temperature range during a temperature-increasing period, the temperature range including at least a part of a temperature range from a temperature lower by 50°C than a crystallization start temperature to a temperature higher by 20°C than the crystallization start temperature and not exceeding a temperature higher by 50°C than the crystallization start temperature, the crystallization start temperature being defined by a differential scanning calorimeter.
  • the magnetic field is applied selectively in the temperature range during the temperature-increasing period.
  • the magnetic field is applied at a strength of 50 kA/m or greater and 300 kA/m or less in the height direction of the magnetic core.
  • the Fe-based nano-crystal alloy ribbon has a thickness of 15 ⁇ m or less and a width of 250 mm or less.
  • the Fe-based nano-crystal alloy or the Fe-based nano-crystal alloy magnetic core are preferably usable for a common mode choke or the like, for which high frequency characteristics are important.
  • One feature of the method for producing an Fe-based nano-crystal alloy and an Fe-based nano-crystal alloy magnetic core in an embodiment according to the present invention is the following.
  • the magnetic field is selectively applied in a specific temperature range during a temperature-increasing period, unlike in the conventional art.
  • the magnetic field is applied in a width direction of a ribbon, namely, in a height direction of a magnetic core.
  • the above-described specific temperature range during the temperature-increasing period in the heat treatment step includes at least a part of a temperature range that is from a temperature lower by 50°C than a crystallization start temperature to a temperature higher by 20°C than the crystallization start temperature but does not exceed a temperature higher by 50°C than the crystallization start temperature.
  • the magnetic field is selectively applied in the width direction of the alloy ribbon that is being heat-treated.
  • the crystallization start temperature is defined by a differential scanning calorimeter.
  • the magnetic field is not applied, for example, at or around the highest temperature reached or during a cooling period after the highest temperature reached.
  • the magnetic field is applied in the above-described period during the temperature-increasing period.
  • a relatively weak magnetic field e.g., less than 50 kA/m
  • a relatively weak magnetic field may be applied temporarily or continuously in an optional period in the heat treatment step.
  • a weak magnetic field of less than 50 kA/m may not be considered as application of a magnetic field.
  • the magnetic field described in the following description is of a level that can influence the magnetic characteristics of a nano-crystal alloy (typically, 50 kA/m or greater and 300 kA/m or less).
  • the specific magnetic permeability ⁇ fluctuates little despite the fluctuation in the strength of the applied magnetic field or fluctuation in the temperature region in which the magnetic field is applied. It has been found that in this case, the specific magnetic permeability ⁇ is easily adjustable at the target frequency, namely, 100 kHz.
  • An alloy of an amorphous structure before being heat-treated has a Curie temperature lower than the crystallization start temperature.
  • the alloy when being nano-crystallized, the alloy has a Curie temperature significantly exceeding the crystallization start temperature. Namely, it is presumed that when a magnetic field is applied during crystallization, the magnetic domain of the alloy is secured along with the crystallization, and thus substantially the same effect as that provided when the alloy is cooled from a temperature higher than, or equal to, the Curie temperature is provided.
  • a magnetic field is applied in at least a part of the temperature-increasing period, more specifically, in at least a part of a temperature range from a temperature lower by 50°C by the crystallization start temperature, which is defined by a differential scanning calorimeter, to a temperature higher by 20°C than the crystallization start temperature.
  • a magnetic field is applied in a temperature-increasing period in which the temperature does not exceed a temperature higher by 50°C than the crystallization start temperature.
  • the temperature range in which the magnetic field is to be applied includes at least a part of a temperature range from a temperature lower by 20°C than the crystallization start temperature, which is defined by the differential scanning calorimeter, to a temperature higher by 10°C than the crystallization start temperature.
  • the upper limit of the temperature at which the magnetic field is to be applied is set to a temperature higher by 50°C than the crystallization start temperature. More preferably, the upper limit of the temperature at which the magnetic field is to be applied is a temperature higher by 40°C than the crystallization start temperature.
  • the temperature-increasing period includes a period in which effective application of a magnetic field is not performed.
  • temperature-increasing period indicates a period before the highest temperature is reached.
  • the “temperature-increasing period” may be a period in which the temperature is being increased, a period in which the temperature is being decreased, or a period in which the temperature is kept constant, as long as being before the highest temperature is reached.
  • the crystallization start temperature is defined by a differential scanning calorimeter. It is difficult to accurately measure the true crystallization start temperature, and it is effective to identify the crystallization start temperature by differential scanning calorimeter (DSC). A temperature at which an exothermic reaction caused by start of nano-crystallization is detected while the temperature is increased is defined as the "crystallization start temperature”. According to the present invention, the measurement by use of a differential scanning calorimeter is performed under the condition that the temperature is increased by 10°C per minute.
  • the heat treatment temperature is preferably controlled such that the temperature distribution in an actual heat treatment furnace is ⁇ 5°C or less in consideration of the capacity of the heat treatment furnace and the amount of heat generation caused by crystallization of an amorphous ribbon that is being heat-treated.
  • Such a manner of control allows the magnetic characteristics of the post-heat treatment alloy to be stabilized.
  • the strength of the magnetic field to be applied is preferably 50 kA/m or greater and 300 kA/m or less.
  • the magnetic field applied is too weak, it is difficult to provide an induced magnetic anisotropy under the actual work conditions.
  • the magnetic field applied is too strong, an excessively large induced magnetic anisotropy tends to be provided.
  • a more preferable range of the strength of the magnetic field to be applied is 60 kA/m or greater and 240 kA/m or less.
  • the time duration in which the magnetic field is to be applied there is no specific limitation as long as the temperature range is as described above.
  • the time duration is practically about 1 to about 180 minutes.
  • a nano-crystallizable Fe-based amorphous alloy usable in the embodiment according to the present invention has a composition represented by, for example, general formula: (Fe 1-a M a ) 100-x-y-z - ⁇ - ⁇ - ⁇ Cu x Si y B z M' ⁇ M" ⁇ X ⁇ (atomic %) (in the formula, M is Co and/or Ni; M' is at least one element selected from the group consisting of Nb, Mo, Ta, Ti, Zr, Hf, V, Cr, Mn and W; M" is at least one element selected from the group consisting of Al, platinum group elements, Sc, rare earth elements, Zn, Sn and Re; X is at least one element selected from the group consisting of C, Ge, P, Ga, Sb, In, Be and As; and a, x, y, z, ⁇ , ⁇ and ⁇ respectively fulfill 0 ⁇ a ⁇ 0.5, 0.1 ⁇ x ⁇ 3, 0 ⁇ y ⁇ 30, 0
  • An alloy having the above-described composition is melted at a temperature higher than, or equal to, a melting point thereof, and rapidly solidified by a single roll method. As a result, a lengthy amorphous alloy ribbon (thin strip) is obtained.
  • the amorphous alloy ribbon preferably has a thickness of 10 to 30 ⁇ m.
  • the thickness is less than 10 ⁇ m, the ribbon has an insufficient mechanical strength and is easily ruptured while being handled.
  • the thickness exceeds 30 ⁇ m a stable amorphous state is not easily obtained.
  • the amorphous alloy ribbon is nano-crystallized and used for a high frequency use as a magnetic core, an eddy current is generated to the ribbon. The loss caused by the eddy current is larger as the ribbon is thicker. Therefore, the thickness of the ribbon is more preferably 10 to 20 ⁇ m.
  • the specific magnetic permeability ⁇ at or around 100 kHz has a larger value as the ribbon is thinner. Therefore, the thickness of the ribbon is still more preferably 15 ⁇ m or less.
  • the amorphous alloy ribbon preferably has a width of 10 mm or greater in consideration of a practical shape of the magnetic core. Slitting a wider alloy ribbon reduces the cost. Therefore, it is preferable that the alloy ribbon is wide on the stage after rapid cooling.
  • the alloy ribbon preferably has a width of 250 mm or less.
  • the alloy ribbon more preferably has a width of 70 mm or less.
  • the heat treatment for nano-crystallization is preferably performed in an inert gas such as nitrogen or the like.
  • the highest temperature to be reached is preferably set to 550 to 600°C.
  • a highest temperature reached that is lower than 550°C or higher than 600°C is not preferable because such a temperature increases the magnetic strain.
  • the alloy may be nano-crystallized even if being kept at the highest temperature reached for 0 minutes (even if not being kept at the highest temperature reached). In consideration of the heat capacity of the entire alloy to be heat-treated and the stability of the characteristics of the alloy, the alloy may be kept at the highest temperature reached for a time duration of greater than 0 minutes to 3 hours or less.
  • a temperature profile in the heat treatment may be, for example, as follows: from room temperature to a temperature at which the nano-crystallization is started or in the vicinity of such a temperature, the temperature is increased relatively rapidly at an increasing rate of 2 to 4°C/min. ; and from a temperature lower by 50°C than the temperature at which the nano-crystallization is started to the highest temperature reached, the temperature is increased at a low rate of 0.2 to 1°C/min.
  • the alloy is preferably cooled at a cooling rate of 2 to 5°C/min. in a temperature region from the highest temperature reached to 200°C. Usually, the alloy may be retrieved to the air after being cooled down to 100°C or lower.
  • the heat treatment step may be performed as follows.
  • the nano-crystallizable Fe-based amorphous alloy ribbon is wound or stacked, and then is heated to a crystallization temperature region and cooled.
  • the magnetic field is applied as described above.
  • the magnetic field may be applied in the height direction of the magnetic core, so that a desired induced magnetic anisotropy is provided.
  • a molten alloy member having a composition, in atomic %, of 1% of Cu, 3% of Nb, 15.5% of Si, 6.5% of B and the remaining part of Fe and unavoidable impurities was rapidly cooled by a single roll method to obtain an Fe-based amorphous alloy ribbon having a width of 50 mm and a thickness of 13 ⁇ m.
  • the Fe-based amorphous alloy ribbon was slit to have a width of 3 mm and then wound into a shape having an outer diameter of 20 mm and an inner dimeter of 10 mm. Thus, ten toroidal magnetic cores were produced.
  • the crystallization start temperature of this alloy measured by differential scanning calorimetry (DSC) was 500°C.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 1 .
  • the magnetic field was continuously applied throughout the temperature range of 440 to 480°C during the temperature-increasing period (temperature range from the temperature lower by 60°C than the crystallization start temperature to the temperature lower by 20°C than the crystallization start temperature).
  • the magnetic field was applied in a width direction of the alloy ribbon, namely, a height direction of the magnetic cores.
  • the magnetic field was set to have a strength of 120 kA/m.
  • the highest temperature reached during the heat treatment was set to be 580°C.
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 27,000 to 30,000.
  • the measurement was performed by use of HP4194A produced by Agilent Technologies under the conditions of an oscillation level of 0.5 V and an average of 16. An insulated covered wire was caused to pierce a central part of each of the toroidal magnetic cores and connected with an input/output terminal for the measurement.
  • Ten toroidal magnetic cores were produced in a similar manner by use of an Fe-based amorphous alloy ribbon having substantially the same composition and size as those in example 1.
  • the produced magnetic cores were heat-treated by the temperature profile in example 1 shown in FIG. 1 with no magnetic field application (with no magnetic field) as shown in FIG. 5 .
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 20,000 to 24,000.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy ribbon as used in example 1.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 2 . Only the temperature range in which the magnetic field was applied was different from that in example 1 ( FIG. 1 ), and the other conditions were substantially the same as those in example 1.
  • the magnetic field was applied in the temperature range of 480 to 520°C (temperature range from the temperature lower by 20°C than the crystallization start temperature to the temperature higher by 20°C than the crystallization start temperature).
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 31,000 to 32,000.
  • the specific magnetic permeability ⁇ at 100 kHz obtained in example 2 is higher than that in example 1. This indicates that application of a magnetic field performed in a temperature range including the crystallization start temperature defined by DSC can further increase the specific magnetic permeability ⁇ at 100 kHz even if the strength of the magnetic field is the same.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy ribbon as used in example 1.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 3 . Only the strength of the magnetic field was different from that in example 2 ( FIG. 2 ), and the other conditions were substantially the same as those in example 2.
  • the magnetic field was applied at a strength of 60 kA/m while the temperature was increased.
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 28,000 to 30,000.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy as used in example 1.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 4 . Only the strength of the magnetic field was different from that in example 2 ( FIG. 2 ), and the other conditions were substantially the same as those in example 2.
  • the magnetic field was applied at a strength of 240 kA/m while the temperature was increased.
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 27,000 to 29,000.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy ribbon as used in example 1.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 6 .
  • the strength of the magnetic field and the time duration of magnetic application were substantially the same as those in examples 1 and 2 ( FIG. 1 and FIG. 2 ), but the magnetic field was applied while the temperature was raised from 560°C to the highest temperature reached of 580°C and then was decreased.
  • the magnetic field was started to be applied at the temperature higher by 60°C than the crystallization start temperature.
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 24,000 to 25,000.
  • the specific magnetic permeability ⁇ at 100 kHz was higher by merely 4, 000 than that in comparative example 1 with no magnetic field application.
  • Comparative example 1 and comparative example 2 were compared against each other regarding the specific magnetic permeability ⁇ at a frequency of 10 kHz.
  • the specific magnetic permeability ⁇ was about 80,000 in comparative example 1 and was about 35,000 in comparative example 2.
  • the specific magnetic permeability ⁇ was higher in comparative example 1. This is presumed to have occurred for the following reason: when a magnetic field is applied in a temperature region higher by a temperature exceeding 50°C than the crystallization start temperature, an excessively large magnetic anisotropy is provided and thus the specific magnetic permeability ⁇ at 100 kHz is low.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy ribbon as used in example 1.
  • the produced magnetic cores were heat-treated and supplied with a magnetic field by a temperature profile and a magnetic field application profile shown in FIG. 7 .
  • the magnetic field was applied throughout the heat treatment step.
  • the magnetic field applied had a strength of 290 kA/m.
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 14,000 to 15,000.
  • a molten alloy member having a composition, in atomic %, of 1% of Cu, 2.5% of Nb, 13.5% of Si, 7.2% of B and the remaining part of Fe and unavoidable impurities was rapidly cooled by a single roll method to obtain an Fe-based amorphous alloy ribbon having a width of 60 mm and a thickness of 18 ⁇ m.
  • the Fe-based amorphous alloy ribbon was slit to have a width of 3 mm and then wound into a shape having an outer diameter of 20 mm and an inner dimeter of 10 mm. Thus, ten toroidal magnetic cores were produced.
  • the crystallization start temperature of this alloy was measured to be 480°C.
  • the produced magnetic cores were heat-treated by the heat treatment profile shown in FIG. 2 .
  • the alloy ribbon was kept at 580°C.
  • the magnetic field was applied in the temperature range of 480 to 520°C while the temperature was increased (temperature range from the crystallization start temperature to the temperature higher by 40°C than the crystallization start temperature).
  • the magnetic field was applied in a width direction of the alloy ribbon, namely, a height direction of the magnetic cores.
  • the magnetic field was set to have a strength of 120 kA/m.
  • the ten post-heat treatment magnetic cores (alloy) were evaluated.
  • the specific magnetic permeability ⁇ at 100 kHz was in the range of 19,000 to 22,000.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy ribbon as used in example 5.
  • the produced magnetic cores were heat-treated by a temperature profile and a magnetic field application profile shown in FIG. 6 with no magnetic field application (with no magnetic field) .
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 17,000 to 18,000.
  • a molten alloy member having a composition, in atomic %, of 5% of Ni, 0.8% of Cu, 2.8% of Nb, 11% of Si, 9. 8% of B and the remaining part of Fe and unavoidable impurities was rapidly cooled by a single roll method to obtain an Fe-based amorphous alloy ribbon having a width of 50 mm and a thickness of 13 ⁇ m.
  • the Fe-based amorphous alloy ribbon was slit to have a width of 3 mm and then wound into a shape having an outer diameter of 20 mm and an inner dimeter of 10 mm.
  • the crystallization start temperature of this alloy was measure to be 480°C.
  • the produced magnetic cores were heat-treated by the heat treatment profile shown in FIG. 2 .
  • the alloy ribbon was kept at 580°C.
  • the magnetic field was applied in the temperature range of 480 to 520°C while the temperature was increased (temperature range from the crystallization start temperature to the temperature higher by 40°C than the crystallization start temperature).
  • the magnetic field was applied in a width direction of the alloy ribbon, namely, a height direction of the magnetic cores.
  • the magnetic field was set to have a strength of 120 kA/m.
  • the ten post-heat treatment magnetic cores (alloy) were evaluated.
  • the specific magnetic permeability ⁇ at 100 kHz was in the range of 15,000 to 17,000.
  • Ten toroidal magnetic cores were produced in a similar manner by use of substantially the same Fe-based amorphous alloy as used in example 6.
  • the produced magnetic cores were heat-treated by a temperature profile and a magnetic field application profile shown in FIG. 6 with no magnetic field application (with no magnetic field) .
  • the ten post-heat treatment magnetic cores had a specific magnetic permeability ⁇ at 100 kHz in the range of 9,000 to 12,000.
  • a molten alloy member having substantially the same alloy composition as that in example 1 (crystallization start temperature: 500°C) was rapidly cooled by a single roll method to obtain an Fe-based amorphous alloy ribbon having a width of 50 mm and a thickness of 18 ⁇ m.
  • the Fe-based amorphous alloy ribbon was slit to have a width of 15 mm and then wound into a shape having an outer diameter of 31 mm and an inner dimeter of 21 mm.
  • four toroidal magnetic cores were produced.
  • the produced magnetic cores were heat-treated by the heat treatment profile shown in FIG. 2 as in example 2.
  • the magnetic field was applied in the temperature range of 480 to 520°C while the temperature was increased.
  • the magnetic field was applied in a width direction of the alloy ribbon, namely, a height direction of the magnetic cores.
  • the magnetic field was set to have a strength of 120 kA/m.
  • the four post-heat treatment magnetic cores (alloy) were evaluated.
  • the specific magnetic permeability ⁇ at 100 kHz was in the range of 28,000 to 29,000.
  • example 2 and example 7 A comparison of example 2 and example 7 against each other confirms that the specific magnetic permeability ⁇ at 100 kHz is slightly higher in example 2 in which the thickness of the Fe-based amorphous alloy ribbon is 15 ⁇ m or less than in example 7 in which the thickness of the Fe-based amorphous alloy ribbon exceeds 15 ⁇ m.
  • the method for producing an Fe-based nano-crystal alloy in the embodiment according to the present invention is applicable to production of a magnetic core of a common mode choke coil, a high frequency transformer and the like.

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EP14849656.5A 2013-09-27 2014-09-22 Verfahren zur herstellung einer eisenbasierten nanokristallinen legierung und verfahren zur herstellung eines magnetischen kerns für die eisenbasierte nanokristalline legierung Active EP3050977B1 (de)

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PCT/JP2014/075070 WO2015046140A1 (ja) 2013-09-27 2014-09-22 Ｆｅ基ナノ結晶合金の製造方法及びＦｅ基ナノ結晶合金磁心の製造方法

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ES2791885T3 (es) * 2014-06-10 2020-11-06 Hitachi Metals Ltd Método para producir núcleo de aleación nanocristalina basada en Fe
EP3441993B1 (de) 2016-02-29 2021-09-15 Hitachi Metals, Ltd. Mehrschichtiger blockkern, mehrschichtiger block, und verfahren zur herstellung eines mehrschichtigen blocks
CN107245673B (zh) * 2017-06-15 2018-12-07 河北工业大学 铁基非晶纳米晶薄带磁体及其制备方法和应用方法
CN107256794B (zh) * 2017-06-22 2019-06-18 东莞市大忠电子有限公司 一种高频逆变纳米晶磁芯及其制备方法
JP7088057B2 (ja) * 2019-02-06 2022-06-21 トヨタ自動車株式会社 合金薄帯の製造方法
JP7074258B2 (ja) * 2019-05-21 2022-05-24 日立金属株式会社 樹脂フィルム付きナノ結晶合金薄帯の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0299498A1 (de) * 1987-07-14 1989-01-18 Hitachi Metals, Ltd. Magnetkern und Verfahren zur Herstellung
US5160379A (en) * 1986-12-15 1992-11-03 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
JPH07278764A (ja) * 1994-04-15 1995-10-24 Hitachi Metals Ltd ナノ結晶合金およびその製造方法ならびにそれを用いた磁心
JP2005187917A (ja) * 2003-12-26 2005-07-14 Hitachi Metals Ltd 軟磁性合金並びに磁性部品

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6479342A (en) * 1986-12-15 1989-03-24 Hitachi Metals Ltd Fe-base soft magnetic alloy and its production
JPH044393A (ja) 1990-04-20 1992-01-08 Hitachi Ltd 配管の制振要素，制振要素を備えた配管及び制振要素を備えた圧力伝達機器
JP2952718B2 (ja) * 1991-03-04 1999-09-27 日本ケミコン株式会社 磁心の熱処理方法
JPH05202452A (ja) * 1992-01-28 1993-08-10 Sumitomo Metal Ind Ltd 鉄基磁性合金の熱処理方法
JP3883642B2 (ja) * 1997-04-28 2007-02-21 アルプス電気株式会社 軟磁性合金の製造方法
KR100473620B1 (ko) * 2000-01-07 2005-03-07 한국전기연구원 철-지르코늄-붕소-은 계 연자성 재료 및 박막의 제조방법
JP4830972B2 (ja) * 2006-08-25 2011-12-07 日立金属株式会社 等方性鉄基希土類合金磁石の製造方法
CN100510114C (zh) * 2007-12-06 2009-07-08 上海大学 一种Fe基大块非晶合金晶化的热处理工艺

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5160379A (en) * 1986-12-15 1992-11-03 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
EP0299498A1 (de) * 1987-07-14 1989-01-18 Hitachi Metals, Ltd. Magnetkern und Verfahren zur Herstellung
JPH07278764A (ja) * 1994-04-15 1995-10-24 Hitachi Metals Ltd ナノ結晶合金およびその製造方法ならびにそれを用いた磁心
JP2005187917A (ja) * 2003-12-26 2005-07-14 Hitachi Metals Ltd 軟磁性合金並びに磁性部品

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2015046140A1 *

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JP6024831B2 (ja) 2016-11-16
JPWO2015046140A1 (ja) 2017-03-09
EP3050977B1 (de) 2018-11-21
CN105593382B (zh) 2017-08-18

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