WO2022264998A1 - ナノ結晶合金薄帯の製造方法、およびナノ結晶合金薄帯 - Google Patents

ナノ結晶合金薄帯の製造方法、およびナノ結晶合金薄帯 Download PDF

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WO2022264998A1
WO2022264998A1 PCT/JP2022/023735 JP2022023735W WO2022264998A1 WO 2022264998 A1 WO2022264998 A1 WO 2022264998A1 JP 2022023735 W JP2022023735 W JP 2022023735W WO 2022264998 A1 WO2022264998 A1 WO 2022264998A1
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alloy ribbon
nanocrystalline alloy
magnetic field
flux density
temperature
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English (en)
French (fr)
Japanese (ja)
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豊永詞
小川雄一
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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
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel 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
    • 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
    • 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

Definitions

  • the present disclosure relates to a method for producing a nanocrystalline alloy ribbon having a nanocrystalline structure, and a nanocrystalline alloy ribbon.
  • Nanocrystalline alloy ribbons with a nanocrystalline structure have excellent magnetic properties and are used in transformers, electronic parts, motors, etc. These transformers, electronic components, motors, etc. are required to be smaller and more efficient. Therefore, there is a demand for further improvement in the properties of soft magnetic alloys used in magnetic cores for these parts (transformers, electronic parts, motors, etc.). Characteristics required for the soft magnetic alloy include high saturation magnetic flux density and low core loss. Among these parts, along with the high frequency of semiconductors, efforts are being made to reduce the size by increasing the operating frequency, and Fe-based amorphous alloys and Fe-based nanocrystalline alloys with low core loss are attracting attention. Therefore, soft magnetic alloys with excellent price, productivity, and heat treatability are required for their commercial spread.
  • the composition formula is Fe100 - abcBaCubM'c
  • M' is at least one element selected from Nb , Mo, Ta, W, Ni, and Co.
  • An alloy having a composition satisfying 10 ⁇ a ⁇ 16, 0 ⁇ b ⁇ 2, and 0 ⁇ c ⁇ 8 and having an amorphous phase is heated at a heating rate of 10 ° C./sec or more, and It describes a method for producing a soft magnetic material that achieves both high saturation magnetization and low coercive force by holding for 0 to 80 seconds above the crystallization start temperature and below the formation start temperature of the Fe—B compound.
  • Patent Document 3 it is represented by Fe 100-xyz A x M y X z , where A is at least one element selected from Cu and Au, M is Ti, Zr, Hf, at least one element selected from V, Nb, Ta, Cr, Mo, and W; X is at least one element selected from B and Si; 4 ⁇ y ⁇ 2.5, 10 ⁇ z ⁇ 20, and the soft magnetic alloy has a saturation magnetic flux density of 1.7 T or more and a coercive force of 15 A/m or less.
  • the soft magnetic material described in Patent Document 1 a soft magnetic material having high saturation magnetization is disclosed.
  • the soft magnetic material described in Patent Document 1 does not contain Si, the SiO 2 film that contributes to the corrosion resistance of the soft magnetic material is not formed on the surface of the material, making it difficult to prevent rust.
  • the soft magnetic alloy described in Patent Document 2 does not have a very high saturation magnetic flux density (Bs).
  • Bs saturation magnetic flux density
  • Example 6 in which the amount of Fe is 84 at %, the saturation magnetic flux density (Bs) is 1.76 T.
  • the heat treatability is insufficient because the amount of B is relatively large.
  • the soft magnetic alloy described in Patent Document 3 contains a large amount of M elements such as expensive Nb, so the price is high.
  • anisotropy is imparted in the casting direction, and the magnetic flux density when a magnetic field of 80 A/m is applied in the casting direction and the magnetic flux density when a magnetic field of 80 A/m is applied in a direction perpendicular to the casting direction.
  • the large ratio makes it unsuitable for applications requiring isotropy.
  • a nanocrystalline alloy ribbon is manufactured by ejecting a molten alloy adjusted to a predetermined alloy composition onto a rotating cooling roll, rapidly cooling and solidifying to manufacture an alloy ribbon, and then heat-treating the alloy ribbon. .
  • the nanocrystalline alloy ribbon is thin, has a predetermined width, and is manufactured as a long ribbon. According to this manufacturing method, anisotropy is likely to be introduced in the casting direction (longitudinal direction), and even after heat treatment, magnetic properties are maintained in the longitudinal direction of the elongated shape and in the width direction orthogonal to the longitudinal direction. tend to be different.
  • nanocrystalline alloy ribbons used in motors are required to have isotropic properties as much as possible.
  • the present disclosure has the following configurations.
  • ⁇ 1> Represented by the compositional formula (Fe 1-x A x ) a Si b B c Cu d Me , where A is at least one of Ni and Co, M is Nb, Mo, V, Zr, Hf and One or more selected from the group consisting of W, in atomic %, 81 ⁇ a ⁇ 86, 0.15 ⁇ b ⁇ 5.0, 12.5 ⁇ c ⁇ 15, 0 ⁇ d ⁇ 1.0, 0 An alloy ribbon satisfying ⁇ e ⁇ 1.0 and 0 ⁇ x ⁇ 0.1 is heat-treated to produce a nanocrystalline alloy ribbon having a structure in which crystal grains having an average grain size of 30 nm or less exist in an amorphous phase.
  • the alloy ribbon With a tension of 10 MPa to 160 MPa applied to the alloy ribbon, the alloy ribbon is conveyed and brought into contact with a heating body so that the temperature rise rate of the alloy ribbon is 100 K / sec or more. , heat-treating the alloy ribbon, When the crystallization temperature of the alloy ribbon is Tx1, the temperature Ta of the heating body is in the range of Tx1 + 85 ° C. to Tx1 + 140 ° C. when e ⁇ 0.4 in the composition formula, and e ⁇ 0 in the composition formula.
  • a method for producing a nanocrystalline alloy ribbon in which the range of Tx1+60° C. to Tx1+100° C. is set at .4.
  • the nanocrystal according to ⁇ 1>, wherein LBr/WBr is 0.2 to 1.8, where WBr is the residual magnetic flux density Br (maximum measured magnetic field Hm 80 A/m) in the width direction perpendicular to the longitudinal direction.
  • the nanocrystalline alloy ribbon has a magnetic flux density B80 of 0.4 T or more when a magnetic field of 80 A/m is applied, and a magnetic flux density B80 of LB80 when a magnetic field of 80 A/m is applied in the longitudinal direction of the nanocrystalline alloy ribbon.
  • LB80/WB80 is 0.3 to 1.7
  • WB80 is the magnetic flux density B80 when a magnetic field of 80 A / m is applied in the width direction orthogonal to the longitudinal direction 2.
  • ⁇ 6> The method for producing a nanocrystalline alloy ribbon according to any one of ⁇ 1> to ⁇ 5>, wherein the temperature of the alloy ribbon is controlled so as not to exceed Ta + 50°C during the heat treatment of the alloy ribbon. . ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the heating body is composed of a plurality of heating units having different temperatures, and the temperature of the heating unit having the highest temperature among the plurality of heating units is the temperature Ta. 2.
  • the nanocrystalline alloy ribbon is represented by the composition formula (Fe 1-x A x ) a Si b B c Cu d Me , where A is at least one of Ni and Co, and M is Nb, Mo, V , Zr, Hf and W, in atomic % 81 ⁇ a ⁇ 86, 0.15 ⁇ b ⁇ 5.0, 12.5 ⁇ c ⁇ 15, 0 ⁇ d ⁇ 1.0, 0 ⁇ e ⁇ 1.0, 0 ⁇ x ⁇ 0.1, and the saturation magnetic flux density Bs is 1.6 T or more
  • the nanocrystalline alloy thin according to ⁇ 8>, wherein L ⁇ m/W ⁇ m is 0.3 to 1.7, where W ⁇ m is the maximum magnetic permeability ⁇ m in the width direction orthogonal to the direction (maximum measured magnetic field Hm 80 A / m). band.
  • the nanocrystalline alloy ribbon has a magnetic flux density B80 of 0.4 T or more when a magnetic field of 80 A/m is applied, and a magnetic flux density B80 of LB80 when a magnetic field of 80 A/m is applied in the longitudinal direction of the nanocrystalline alloy ribbon. Any one of ⁇ 8> to ⁇ 10> where LB80/WB80 is 0.3 to 1.7, where WB80 is the magnetic flux density B80 when a magnetic field of 80 A / m is applied in the width direction orthogonal to the longitudinal direction 2.
  • ⁇ 12> The nanocrystalline alloy ribbon according to any one of ⁇ 8> to ⁇ 11>, which has a thickness of 15 ⁇ m or more and a width of 5 mm or more.
  • nanocrystalline alloy ribbon according to any one of ⁇ 8> to ⁇ 12> which has a space factor of 86% or more.
  • nanocrystalline alloy ribbon according to any one of ⁇ 8> to ⁇ 13> which has a saturation magnetostriction of 30 ppm or less.
  • a nanocrystalline alloy ribbon having excellent magnetic properties and isotropy it is possible to provide a nanocrystalline alloy ribbon having excellent magnetic properties and isotropy.
  • FIG. 1 shows an example of an in-line annealing apparatus that can be used for the heat treatment of the present disclosure
  • FIG. 2 is a diagram plotting examples and comparative examples of the present disclosure with Ta ⁇ Tx1 (° C.) on the X-axis and tension (MPa) on the Y-axis.
  • a numerical range indicated using "-" indicates a range that includes the numerical values described before and after "-" as lower and upper limits, respectively.
  • upper or lower limits described in a certain numerical range may be replaced with upper or lower limits of other numerical ranges described step by step.
  • upper or lower limits described in a certain numerical range may be replaced with values shown in Examples.
  • a combination of two or more preferred aspects is a more preferred aspect.
  • the nanocrystalline alloy ribbon of the present disclosure is represented by the composition formula ( Fe1 - xAx ) aSibBcCudMe , where A is at least one of Ni and Co, and M is Nb , Mo , V, Zr, Hf and W, in atomic % 81 ⁇ a ⁇ 86, 0.15 ⁇ b ⁇ 5.0, 12.5 ⁇ c ⁇ 15, 0 ⁇ d ⁇ 1.0, 0 ⁇ e ⁇ 1.0, and 0 ⁇ x ⁇ 0.1.
  • Fe is 81% or more and 86% or less in atomic %.
  • a high saturation magnetic flux density can be obtained by setting the Fe content to 81% or more. It is preferably 82% or more, more preferably 82.5% or more, still more preferably 83% or more, still more preferably 83.5% or more, still more preferably 84% or more. Further, if the Fe content exceeds 86%, it becomes difficult to amorphize, so the Fe content is made 86% or less. Preferably, it is 85.5% or less.
  • Si silicon is 0.15% or more and 5.0% or less in atomic %.
  • Si an oxide film of SiO 2 with a thickness of several tens of nanometers can be formed on the alloy surface. This can improve the corrosion resistance of the nanocrystalline alloy ribbon.
  • 0.15% or more of Si is contained. Preferably it is 1.0% or more. If the Si content exceeds 5.0%, it becomes difficult to obtain a high saturation magnetic flux density, and it becomes difficult to increase the thickness of the alloy ribbon. Therefore, the Si content is set to 5.0% or less. It is preferably 4% or less, more preferably 3% or less, and still more preferably 2% or less.
  • B (boron) is 12.5% or more and 15% or less in atomic %. If the B content is less than 12.5%, it becomes difficult to form an amorphous material, so the B content is made 12.5% or more. It is preferably 13.0% or more, more preferably 13.5% or more. When the B content exceeds 15%, the difference between the bccFe( ⁇ Fe) crystallization start temperature and the FeB precipitation start temperature becomes small, narrowing the temperature range in which heat treatment is possible. For this reason, it becomes difficult to obtain a uniform and fine nanocrystalline structure capable of obtaining a core loss of 25 W/kg or less at 1 T, 1 kHz. Accordingly, the content of B is set to 15% or less. It is preferably 14.5% or less, more preferably 14.4% or less, further preferably 14.0% or less.
  • Cu copper
  • the content of Cu may be 0%, but the inclusion of Cu facilitates obtaining a uniform and fine nanocrystalline structure.
  • the Cu content is preferably 0.05% or more. It is more preferably 0.1% or more, still more preferably 0.2% or more, still more preferably 0.4% or more, still more preferably 0.5% or more. If the Cu content exceeds 1.0%, embrittlement tends to occur, making it difficult to increase the thickness of the nanocrystalline alloy ribbon. Therefore, the content of Cu is set to 1.0% or less. It is preferably 0.9% or less, more preferably 0.85% or less, still more preferably 0.7% or less, still more preferably 0.6% or less.
  • the M element is one or more elements selected from the group consisting of Nb, Mo, V, Zr, Hf and W, and is 0% or more and 1.0% or less in terms of atomic %.
  • the M element may be 0%, but by including the M element, the precipitation start temperature of the FeB compound that significantly deteriorates the soft magnetism can be shifted to a higher temperature side.
  • the difference between the bccFe ( ⁇ Fe) crystallization start temperature (also referred to as the crystallization temperature) and the FeB precipitation start temperature can be widened, which has the effect of widening the range of the optimum heat treatment temperature and relaxes the heat treatment conditions.
  • the content of M element is set to 1.0% or less. It is preferably 0.9% or less, more preferably 0.8% or less, still more preferably 0.7% or less, still more preferably 0.6% or less. Also, the M element is preferably less than 0.4%, more preferably 0.3% or less, and further preferably 0.25% or less.
  • part of Fe may be replaced with at least one element of Ni and Co.
  • Fe 1-x A x A is at least one of Ni and Co, and x is 0.1 or less.
  • the nanocrystalline alloy ribbon of the present disclosure may contain C (carbon).
  • C is preferably 1% by mass or less.
  • the nanocrystalline alloy ribbon of the present disclosure may contain impurities other than the above elements.
  • Impurities include, for example, S (sulfur), O (oxygen), N (nitrogen), Cr, Mn, P, Ti, and Al.
  • S sulfur
  • O oxygen
  • N nitrogen
  • Cr manganese
  • Mn manganese
  • P titanium
  • Al aluminum
  • the S content is preferably 200 mass ppm or less
  • the O content is preferably 5000 mass ppm or less
  • the N content is preferably 1000 mass ppm or less.
  • the total content of these impurities is preferably 0.5% by mass or less.
  • an element corresponding to an impurity may be added within the above range.
  • the nanocrystalline alloy ribbon of the present disclosure has a structure in which crystal grains having an average grain size of 30 nm or less exist in the amorphous phase.
  • a structure in which crystal grains having an average grain size of 30 nm or less exist in an amorphous phase is also called a nanocrystalline structure.
  • the nanocrystalline alloy ribbon of the present disclosure is obtained by ejecting a molten alloy having the alloy composition described above onto a rotating cooling roll, rapidly cooling and solidifying it on the cooling roll to obtain an alloy ribbon, and heat-treating the alloy ribbon.
  • the alloy ribbon obtained by quenching and solidifying the molten alloy is in an amorphous state and is an amorphous alloy ribbon.
  • a nanocrystalline alloy ribbon is obtained by heat-treating the amorphous alloy ribbon (amorphous alloy ribbon).
  • the amorphous alloy ribbon may have a crystalline phase composed of fine crystals.
  • the molten alloy can be obtained by blending each element source (pure iron, ferroboron, ferrosilicon, etc.) for the desired alloy composition, heating in an induction heating furnace, and melting above the melting point to obtain a molten alloy.
  • An alloy ribbon can be obtained by ejecting a molten alloy from a slit-shaped nozzle having a predetermined shape onto a rotating cooling roll and rapidly solidifying the molten alloy on the cooling roll.
  • the cooling roll can have an outer diameter of 350 to 1000 mm, a width of 100 to 400 mm, and a peripheral speed of rotation of 20 to 35 m/sec.
  • This cooling roll is internally provided with a cooling mechanism (such as water cooling) for suppressing an increase in the temperature of the outer peripheral portion.
  • the outer peripheral portion of the cooling roll is made of a Cu alloy having a thermal conductivity of 120 W/(m ⁇ K) or more.
  • the thermal conductivity of the outer peripheral portion is set to 120 W/(m ⁇ K) or more.
  • the cooling rate when the molten alloy is cast into the alloy ribbon can be increased.
  • the embrittlement of the alloy ribbon is suppressed, making it possible to increase the thickness of the alloy ribbon, and surface crystallization during casting is suppressed, thereby suppressing coarsening of crystal grains during heat treatment. , iron loss can be reduced.
  • the thermal conductivity of the outer peripheral portion is preferably 150 W/(m ⁇ K) or more, more preferably 180 W/(m ⁇ K) or more.
  • the thermal conductivity of the outer peripheral portion is preferably 150 W/(m ⁇ K) or more.
  • the outer peripheral portion of the cooling roll is the portion in contact with the molten alloy, and the thickness thereof may be about 5 to 15 mm.
  • a nanocrystalline alloy ribbon is obtained by heat-treating the alloy ribbon produced by the above quenching method.
  • the method for manufacturing the nanocrystalline alloy ribbon of the present disclosure is characterized by the heat treatment method.
  • the alloy ribbon is conveyed while a tension of 10 MPa to 160 MPa is applied to the alloy ribbon, and the alloy ribbon is brought into contact with a heating body so that the temperature rise rate of the alloy ribbon is 100 K. / seconds or more.
  • the crystallization temperature of the alloy ribbon is Tx1
  • the temperature Ta of the heating element is in the range of Tx1 + 85 ° C. to Tx1 + 140 ° C.
  • the crystallization temperature of the alloy ribbon is the crystallization start temperature of bccFe ( ⁇ Fe).
  • the alloy ribbon is subjected to heat treatment by applying tension to the alloy ribbon, conveying the alloy ribbon, and heating the alloy ribbon by bringing it into contact with a heating body.
  • the tension, the temperature of the heating element, and the heating rate of the alloy ribbon are important requirements.
  • the effect of obtaining isotropic magnetic properties can be expected by applying tension and performing heat treatment at a high heating rate.
  • the tension is set to 10 MPa to 160 MPa. It is preferably 30 MPa or more. More preferably, it is 34 MPa or more. Moreover, it is preferably 150 MPa or less. More preferably, it is 145 MPa or less.
  • the temperature Ta of the heater has a different preferred temperature range depending on the composition. It was also found that the temperature Ta of the heating element can be set by a relational expression with the crystallization temperature of the alloy ribbon (the crystallization start temperature of bccFe( ⁇ Fe)) Tx1.
  • the temperature Ta of the heating element is set in the range of Tx1+85.degree. C. to Tx1+140.degree. It is preferably Tx1+90° C. or higher, more preferably Tx1+95° C. or higher. It is preferably Tx1+120° C. or less, more preferably Tx1+115° C. or less.
  • the temperature Ta of the heater is set in the range of Tx1+60.degree. C. to Tx1+100.degree.
  • the temperature Ta of the heater is set in the range of Tx1+60.degree. C. to Tx1+100.degree.
  • the FeB precipitation start temperature Tx2 exists at a temperature higher than the crystallization temperature.
  • the alloy ribbon reaches the FeB precipitation start temperature, crystals become coarse and FeB, which degrades the magnetic properties, is precipitated. Therefore, it is necessary to perform the heat treatment so as not to reach the FeB precipitation start temperature.
  • the crystallization temperature and FeB precipitation start temperature of the alloy ribbon can be obtained as follows.
  • the crystallization temperature and the FeB precipitation start temperature change depending on the temperature increase rate, but the upper limit of the temperature increase rate of a general thermal analysis apparatus is about 2 ° C./second, and the temperature increase rate during the heat treatment of the present disclosure can be measured. Since it is not possible, the value at a temperature increase rate of 50° C./sec was obtained by the method described below and used as the crystallization temperature and the FeB precipitation start temperature.
  • the heating rate of the alloy ribbon shall be 100 K/sec or higher. This temperature increase rate was calculated by finding the slope of the tangential line near the heat treatment temperature Ta when the temperature was raised. It is preferably 300 K/sec or higher, more preferably 500 K/sec or higher.
  • the upper limit may be an upper limit that is set within a possible range for the apparatus and process conditions. For example, it can be 4000 K/sec or less. It is preferably 3000 K/sec or less, more preferably 2500 K/sec or less.
  • the alloy ribbon is heat treated while being transported. Since the alloy ribbon is formed in a long length, heat treatment can be performed on the long alloy ribbon efficiently by carrying out the heat treatment while transporting the alloy ribbon.
  • the contact time between the alloy ribbon and the heater is preferably 0.5 seconds to 60 seconds.
  • the transport speed of the alloy ribbon is preferably 3 m/min to 300 m/min. More preferably, it is 200 m/min or less.
  • the heating body may be composed of a plurality of heating parts with different temperatures.
  • the temperature of the heating portion having the highest temperature among the plurality of heating portions is assumed to be the above-described temperature Ta.
  • the alloy ribbon may generate self-heating as it crystallizes during heat treatment. As described above, when the temperature of the alloy ribbon reaches the FeB precipitation initiation temperature, the desired magnetic properties of the nanocrystalline alloy ribbon cannot be obtained. Further, even if the temperature does not reach the FeB precipitation start temperature, if the temperature rises too much, the grain size growth is accelerated and the iron loss deteriorates.
  • the temperature Ta of the heating element is the highest temperature for heating the alloy ribbon when there is no temperature rise due to self-heating.
  • the heating temperature of the alloy ribbon exceeds the temperature Ta of the heating element. At this time, it is preferable to suppress an excessive temperature rise. In the present disclosure, it is preferable to control the temperature of the alloy ribbon so as not to exceed Ta+50° C. due to temperature rise due to self-heating.
  • FIG. 1 shows an in-line annealing apparatus described in International Publication No. WO2019/009309.
  • the in-line annealing apparatus shown in FIG. 1 can be used for the heat treatment of the present disclosure.
  • the in-line annealing apparatus 100 shown in FIG. 10 a cooling plate 32 for cooling the alloy ribbon 10 heated by the heating body 22, and a winding roller 14 for winding the alloy ribbon 10 cooled by the cooling plate 32.
  • winding device In FIG. 1, the arrow R indicates the running direction of the alloy ribbon 10 .
  • the heating element 22 includes a first plane 22S on which the alloy strip 10 unwound from the unwinding roller 12 travels while being in contact therewith.
  • the heating element 22 heats the alloy ribbon 10 running on the first plane 22S while contacting the first plane 22S via the first plane 22S.
  • the heating body 22 may be a combination of a plurality of heating units that can be set to different temperatures, or may be configured to be set to a plurality of heating temperatures while integrating the above-described first plane 22S portion. With these, the heating body can be composed of a plurality of heating portions.
  • a heating element 22 is housed in the heating chamber 20 .
  • the heating chamber 20 may have a heat source for controlling the temperature of the heating chamber, in addition to the heat source for the heating element 22 .
  • the cooling plate 32 includes a second plane 32S on which the alloy ribbon 10 travels in contact, as shown in the encircled enlarged portion. The cooling plate 32 lowers the temperature of the alloy ribbon 10 running on the second plane 32S while contacting the second plane 32S via the second plane 32S.
  • a cooling plate 32 is housed in the cooling chamber 30 .
  • the take-up roller 14 has a rotating mechanism (for example, a motor) that rotates in the direction of arrow W. The rotation of the take-up roller 14 causes the alloy ribbon 10 to be taken up at a desired speed.
  • a rotating mechanism for example, a motor
  • the in-line annealing device 100 includes a guide roller 41, a dancer roller 60 (one of tension adjusting devices), a guide roller 42, and a , a pair of guide rollers 43A and 43B. Adjustment of the tension is also performed by controlling the motion of the unwind roller 12 and the take-up roller 14 .
  • Dancer roller 60 is provided so as to be movable in the vertical direction (the direction of the double-sided arrow in FIG. 1).
  • the tension of the alloy ribbon 10 can be adjusted by adjusting the position of the dancer roller 60 in the vertical direction (the direction of the arrow on both sides).
  • the dancer roller 62 is also the same.
  • a plurality of openings may be provided in the first plane of the heating body 22 to allow suction, thereby improving the adhesion between the alloy ribbon and the heating body.
  • the material of the heating body includes copper, copper alloys (bronze, brass, etc.), aluminum, iron, iron alloys (stainless steel, etc.), and the like. Among them, copper, a copper alloy, or aluminum is preferable because of its high thermal conductivity (heat transfer coefficient).
  • the heating body may be plated with Ni plating, Ag plating, or the like.
  • the nanocrystalline alloy ribbon of the present disclosure is obtained by the manufacturing method described above, has the composition described above, has excellent magnetic properties, and is isotropic.
  • the nanocrystalline alloy ribbon of the present disclosure is a nanocrystalline alloy ribbon having a structure in which crystal grains having an average grain size of 30 nm or less exist in an amorphous phase, has a saturation magnetic flux density Bs of 1.6 T or more, and is a nanocrystalline
  • LBr/WBr is 0.2 to 1.8.
  • LBr/WBr is preferably 0.4 to 1.6, more preferably 0.6 to 1.4, and more preferably 0.8 to 1.2.
  • the nanocrystalline alloy ribbon of the present disclosure preferably has a core loss of 25 W/kg or less at 1 kHz and 1 T. It is more preferably 20 W/kg or less, more preferably 15 W/kg or less.
  • the saturation magnetic flux density Bs is preferably 1.65 T or more, more preferably 1.7 T or more, and more preferably 1.75 T or more.
  • L ⁇ m/W ⁇ m is preferably 0.3 to 1.7.
  • L ⁇ m/W ⁇ m is more preferably 0.6 to 1.4, more preferably 0.8 to 1.2.
  • LE/WE is 0.2. ⁇ 1.8 is preferred.
  • LE/WE is more preferably 0.4 to 1.6, more preferably 0.6 to 1.4, and more preferably 0.8 to 1.2.
  • the nanocrystalline alloy ribbon of the present disclosure has a magnetic flux density B80 of 0.4 T or more when a magnetic field of 80 A / m is applied, and a magnetic flux density B80 of 0.4 T or more when a magnetic field of 80 A / m is applied in the longitudinal direction of the nanocrystalline alloy ribbon.
  • LB80 is LB80 and WB80 is the magnetic flux density B80 when a magnetic field of 80 A/m is applied in the width direction orthogonal to the longitudinal direction
  • LB80/WB80 is preferably 0.3 to 1.7.
  • LB80/WB80 is more preferably 0.6 to 1.4, more preferably 0.8 to 1.2.
  • the nanocrystalline alloy ribbon of the present disclosure preferably has a thickness of 15 ⁇ m or more. Furthermore, it is preferably 30 ⁇ m or more. When the thickness is 15 ⁇ m or more, it is possible to reduce the number of man-hours and manufacturing costs when laminating nanocrystalline alloy ribbons to produce a magnetic core. More preferably, it is 32 ⁇ m or more. Further, ribbons having a plate thickness of about 15 to 25 ⁇ m are preferable for applications that require a lower iron loss in a high frequency band exceeding 1 kHz. Moreover, it is preferable that the width is 5 mm or more. The width is more preferably 10 mm or more, more preferably 100 mm or more. More preferably, it is 200 mm or more.
  • the nanocrystalline alloy ribbon of the present disclosure preferably has a space factor of 86% or more.
  • the space factor is preferably 88% or more, more preferably 90% or more. Due to the high lamination factor, when the soft magnetic alloy ribbons are stacked, even if the number of lamination is the same, the lamination thickness can be made thinner than the alloy ribbons with a low lamination factor. Contributes to miniaturization and miniaturization of parts.
  • the space factor can be measured by the following method based on JIS C 2534:2017.
  • LF (%) sample weight (g)/density (g/cm 3 )/hmax ( ⁇ m)/sample length (240 cm)/ribbon width (cm) ⁇ 10000
  • the density (g/cm 3 ) is the density of the alloy ribbon after heat treatment, and was set to 7.5 g/cm 3 .
  • the saturation magnetostriction is preferably 30 ppm or less.
  • the nanocrystalline alloy ribbon of the present disclosure can be used to form magnetic cores for use in transformers, electronic components, motors, and the like, thereby obtaining magnetism with excellent properties.
  • the magnetic core can be formed by stacking an alloy ribbon cut into a predetermined shape, winding the alloy ribbon, or stacking and bending the alloy ribbon.
  • the magnetic core and windings of the present disclosure may be combined with a magnetic core made of another magnetic material.
  • Example 1 Element sources were blended so as to have each composition shown in Table 1, heated to 1300 ° C. to prepare a molten alloy, and the molten alloy was placed on a cooling roll with an outer diameter of 400 mm and a width of 200 mm rotating at a peripheral speed of 30 m / sec. The mixture was ejected and rapidly solidified on a cooling roll to produce an alloy ribbon.
  • the outer peripheral portion of the cooling roll is made of a Cu alloy with a thermal conductivity of 150 W/(m ⁇ K), and has a cooling mechanism for controlling the temperature of the outer peripheral portion.
  • the produced alloy ribbon was in an amorphous state and was an amorphous alloy ribbon.
  • the crystallization temperature (the crystallization start temperature of bccFe( ⁇ Fe)) Tx1 and the FeB precipitation start temperature Tx2 were measured by the method described above, and the results are shown in Table 1.
  • the alloy ribbon after the heat treatment was a nanocrystalline alloy ribbon having a structure in which crystal grains with an average grain size of 30 nm or less existed in the amorphous phase.
  • a magnetic field of 8000 A/m is applied to the heat-treated veneer sample using a DC magnetization property tester manufactured by Metron Giken, and the maximum magnetic flux density at that time is measured and defined as Bs. Since the nanocrystalline alloy ribbon of the present disclosure is relatively easily saturated, it is saturated at the time of applying a magnetic field of 8000 A / m. Bs is represented by B8000 .
  • Magnetic flux density B80 A magnetic field of 80 A/m was applied to the nanocrystalline alloy ribbon using a DC magnetization property tester manufactured by Metron Giken, and the maximum magnetic flux density at that time was defined as B80. In addition, a magnetic field of 80 A/m is applied in the longitudinal direction (casting direction) of the nanocrystalline alloy ribbon and in the width direction perpendicular to the longitudinal direction, the maximum magnetic flux densities at that time are LB80 and WB80, respectively, and the ratio LB80/WB80 is calculated. , isotropy was evaluated.
  • [Maximum magnetic permeability ⁇ m] A magnetic field up to 80 A/m is applied to the nanocrystalline alloy ribbon by a Metron Giken DC magnetization property tester, and the maximum value of the quotient of the magnetic flux density and the magnetic field at that time is the maximum magnetic permeability ⁇ m, and the longitudinal direction (casting direction)
  • the maximum magnetic permeability measured in the width direction orthogonal to the longitudinal direction was L ⁇ m and W ⁇ m, respectively, and the ratio L ⁇ m/W ⁇ m was calculated to evaluate the isotropy.
  • a magnetic field up to 800 A/m is applied to the nanocrystalline alloy ribbon using a Metron Giken DC magnetization property tester, and the value obtained by subtracting the area of the magnetic flux density-magnetic field curve from the product of the maximum magnetic flux density and the maximum measured magnetic field at that time.
  • the anisotropic energy is E, and the anisotropic energies measured in the longitudinal direction (casting direction) and in the width direction perpendicular to the longitudinal direction are LE and WE, respectively. done.
  • samples with LBr/WBr in the range of 0.2 to 1.8 were tested for materials A, B, D, and G, which are materials with e ⁇ 0.4 in the composition formula.
  • a sample outside the range is a comparative example, the example is ⁇ , the comparative example is ⁇ , the X axis is Ta-Tx1 (° C.), and the Y axis is tension (MPa).
  • a plotted figure is shown in FIG. As shown in FIG. 2, when Ta-Tx1 is 81° C. or less, it is a comparative example, and when it exceeds 81° C., it is an example.
  • a highly isotropic nanocrystalline alloy ribbon can be obtained by setting the tension to 10 MPa to 160 MPa and setting the temperature Ta of the heating body to the range of Tx1+85° C. to Tx1+140° C. It is understood that
  • L ⁇ m/W ⁇ m is within the range of 0.3 to 1.7.
  • LE/WE is within the range of 0.2 to 1.8.
  • LB80/WB80 is within the range of 0.3 to 1.7.
  • the nanocrystalline alloy ribbons of the examples of the present disclosure have an iron loss of 10 W / kg or less, and a low-loss nanocrystalline alloy ribbon with an iron loss of 25 W / kg or less. have been obtained. Moreover, a saturation magnetostriction of 15 ppm or less has been obtained, and a nanocrystalline alloy ribbon with a saturation magnetostriction of 30 ppm or less has been obtained.
  • Table 4 shows self-heating. This self-heating is a value (temperature of the alloy ribbon - Ta) that the temperature of the alloy ribbon exceeds the heating temperature (temperature Ta of the heating element) due to the heat generated by the crystallization of the alloy ribbon. According to the examples of the present disclosure, the temperature can be controlled within a range not exceeding Ta+50°C.
  • Example 2 Using materials B and G shown in Table 1, nanocrystalline alloy ribbons were produced in the same manner as in Example 1. Table 5 shows the tension, the temperature Ta of the heating element, the heating rate of the ribbon, the contact time with the heating element, the crystal volume ratio, and the average grain size.
  • the average particle size is the average particle size of the nanocrystals.
  • the average particle size of the nanocrystals was calculated from the above Scherrer's formula (Equation 1). It can be seen that the examples of the present disclosure have an average particle size of 30 nm or less. Therefore, the nanocrystalline alloy ribbon of the present disclosure has a structure in which crystal grains with an average grain size of 30 nm or less exist in the amorphous phase.
  • the crystal volume ratio is the volume ratio of crystal grains (nanocrystals) having an average grain size of 30 nm or less.
  • the portion other than the nanocrystals is amorphous.
  • the crystalline volume fraction is the ratio of the integrated intensity of nanocrystals to the integrated intensity of (crystalline + amorphous).
  • the integrated intensity of the peak indicated by the nanocrystal and the halo pattern indicated by the amorphous is obtained by performing peak decomposition using the pseudo-Voigt function for the X-ray diffraction pattern, and the sum of the integrated intensities of all the peaks indicated by the nanocrystal is Ic, Assuming that the sum of integrated intensities of all halo patterns exhibited by the amorphous is Ia, the volume ratio V can be obtained from the following formula (Equation 2).
  • the temperature rise rate of each sample is 100 K/sec or more.
  • Example 3 A nanocrystalline alloy ribbon was produced in the same manner as in Example 1 using material B shown in Table 1.
  • the heating element has a structure having two heating portions.
  • the heating element (heating plate) 22 shown in FIG. 1 has a structure capable of setting two temperatures, with the temperature of the first portion set at T1 and the second temperature set at T2. Then, of T1 and T2, the higher temperature was taken as Ta.
  • Table 6 shows the tension of each sample, the temperatures T1, T2 and Ta of the heating element, and the transport speed of the alloy ribbon.
  • Table 7 shows the properties of each sample produced under these conditions.

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JPS63302504A (ja) * 1987-06-02 1988-12-09 Hitachi Metals Ltd 磁心およびその製造方法
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