EP0342921B1 - Weichmagnetische Legierung auf Eisenbasis - Google Patents

Weichmagnetische Legierung auf Eisenbasis Download PDF

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Publication number
EP0342921B1
EP0342921B1 EP89304925A EP89304925A EP0342921B1 EP 0342921 B1 EP0342921 B1 EP 0342921B1 EP 89304925 A EP89304925 A EP 89304925A EP 89304925 A EP89304925 A EP 89304925A EP 0342921 B1 EP0342921 B1 EP 0342921B1
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EP
European Patent Office
Prior art keywords
alloy
atomic
magnetic
crystal grains
soft magnetic
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Expired - Lifetime
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EP89304925A
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English (en)
French (fr)
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EP0342921A3 (en
EP0342921A2 (de
Inventor
Takao C/O Intellectual Property Division Sawa
Masami C/O Intellectual Property Division Okamura
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Toshiba Corp
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Toshiba Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—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 hard-magnetic materials
    • H01F1/04—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 hard-magnetic materials metals or alloys
    • 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

Definitions

  • This invention relates to Fe-based, soft magnetic alloys.
  • iron cores of crystalline materials such as permalloy or ferrite have been employed in high frequency devices such as switching regulators.
  • the resistivity of permalloy is low, so it is subject to large core loss at high frequency.
  • the core loss of ferrite at high frequencies is small, the magnetic flux density is also small, at best 5,000 G. Consequently, in use at high operating magnetic flux densities, ferrite becomes close to saturation and as a result the core loss is increased.
  • transformers that are used at high frequency such as the power transformers employed in switching regulators, smoothing choke coils, and common mode choke coils.
  • the size is reduced, the operating magnetic flux density must be increased, so the increase in core loss of the ferrite becomes a serious practical problem.
  • amorphous magnetic alloys i.e., alloys without a crystal structure
  • Such amorphous magnetic alloys are typically base alloys of Fe, Co, Ni, etc., and contain metalloids as elements promoting the amorphous state, (P, C, B, Si, Al, and Ge, etc.).
  • Co-based, amorphous alloys also have been used in magnetic components for electronic devices such as saturable reactors, since they have low core loss and high squareness ratio in the high frequency region.
  • the cost of Co-based alloys is comparatively high making such materials uneconomical.
  • Fe-based amorphous alloys constitute cheap soft magnetic materials and have comparatively large magnetostriction, they suffer from various problems when used in the high frequency region and are inferior to Co-based amorphous alloys in respect of both core loss and permeability.
  • Co-based amorphous alloys have excellent magnetic properties, they are not industrially practical due to the high cost of such materials.
  • the object of this invention is to provide an Fe-based, soft magnetic alloy having high saturation magnetic flux density in the high frequency region and with excellent soft magnetic characteristics.
  • an Fe-based soft magnetic alloy having fine crystal grains, as described in the following formula (I) Fe 100-a-b-c-d M a M' b Z c N d (I) where M is at least one element from the following: Cu, Ag, Au, Zn, Sn, Pb, Sb, and Bi; M' is at least one element from the following: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, or Mn, Co, Ni, and Al; Z is at least one element from the following: Si, P, and B; and wherein a, b, c and d, expressed in atomic % are as follows: 0.01 ⁇ a ⁇ 5 0.1 ⁇ b ⁇ 10 15 ⁇ c ⁇ 28 0 ⁇ d ⁇ 8.
  • Fine crystal grains are present in the alloy to the extent of 30%, in the range of 5 to 30 nm (50 to 300 ⁇ ) or more in terms of area ratio. At least 80% of the fine crystal grains should be of a crystal grain size of 5 to 30 nm (50 ⁇ to 300 ⁇ ).
  • area ratio of the fine crystal grains as used herein means the ratio of the surface of the fine grains to the total surface in a plane of the alloy as measured, for example, by photomicrograph or by microscopic examination of ground and polished specimens.
  • composition thereof should be balanced and within the limits as hereinafter discussed.
  • An alloy in accordance with the invention contains: Fe; N; at least one of Cu, Ag, Au, Zn, Pb, Sb, and Bi; at least one of element from the group Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, and Al; and at least one of Si, P, and B; in accordance with the formula (I) as defined above.
  • alloys according to the invention contain the aforesaid components in the specified amounts to obtain the advantageous characteristics of the new alloys.
  • M is at least one of: Cu, Ag, Au, Zn, Sn, Pb, Sb and Bi. These elements can be effective in increasing corrosion resistance, preventing coarsening of the crystal grains, and in improving soft magnetic properties such as core loss and permeability. However, if there is too little, the benefit of its addition is not obtained. On the other hand, if there is too much M, deterioration of magnetic properties results. A range of 0.01 to 5 atomic % is therefore selected. Preferably the amount is 0.5 to 3 atomic %.
  • M' is an element which can be effective in making the crystal grain size uniform and in improving the soft magnetic properties by reducing magnetostriction and magnetic anisotropy. It can also be effective in improving the magnetic properties in respect of temperature change. However, if the amount of M' is too small, the benefit of the addition is not obtained. On the other hand, if the amount is too large, the saturation magnetic flux density is lowered. An amount of M' in the range of 0.1 to 10 atomic % is therefore selected. Preferably the amount is 1 to 7 atomic % and even more preferably 1.5 to 5 atomic %.
  • the various additive elements in M' can have the following respective effects: in the case of Japanese Group IVa elements namely Ti, Zr and Hf, increase of the range of heat treatment conditions for obtaining optimum magnetic properties; in the case of Japanese Group Va elements namely V, Nb and Ta, and Mn, increase in resistance to embrittlement and increase in workability such as by cutting; in the case of Japanese Group VIa elements, namely Cr, Mo and W improvement of corrosion resistance and surface shape; in the case of A1, increased fineness of the crystal grains and reduction of magnetic anisotropy, thereby improving magnetostriction and soft magnetic properties.
  • Z comprises elements that can be effective in making the alloy amorphous during manufacture, or in directly segregating fine crystals. If the amount is too small, the benefit of superquenching in manufacture is difficult to obtain and the above condition is not obtained. On the other hand, if the amount of "Z" is too great, the saturation magnetic flux density becomes low, also making the above condition difficult to obtain, with the result that superior magnetic properties are not obtained.
  • An amount in the range 15 to 28 atomic % is therefore selected. Preferably the range is 18 to 26 atomic %.
  • the ratio of Si/B and/or Si/P is preferably more than 1.
  • Nitrogen is included because it can be effective in expanding the range of heat treatment conditions in order to obtain optimum magnetic properties. However, if there is too much N, fine crystals are difficult to obtain, so the amount is specified as being less than 8 at. %. Preferably it is less than 6 atomic %, and even more preferably less than 4 atomic %.
  • the Fe-based soft magnetic alloy of this invention may be obtained by the following method: An amorphous alloy thin strip is obtained by liquid quenching, then heat treated for one minute to ten hours, preferably ten minutes to five hours at a temperature of 50C o below to 120C o above the crystallization temperature of the amorphous alloy, preferably 30C o below to 100C o above, to segregate the required fine crystals. Alternatively, direct segregation of the fine crystals can be accomplished by controlling quenching rate in the liquid quenching method.
  • Fe-based soft magnetic alloys of this invention can have excellent soft magnetic properties at high frequency. They may exhibit excellent properties as an alloy for magnetic materials for magnetic components such as magnetic cores used at radio frequency, such as, for example, magnetic heads, thin film heads, radio frequency transformers including transformers for high power use, saturable reactors, common mode choke coils, normal mode choke coils, high voltage pulse noise filters, and magnetic switches used in laser power sources, and the like, and for sensors of various types, such as power source sensors, directions sensors, and security sensors, and the like.
  • magnetic components such as magnetic cores used at radio frequency, such as, for example, magnetic heads, thin film heads, radio frequency transformers including transformers for high power use, saturable reactors, common mode choke coils, normal mode choke coils, high voltage pulse noise filters, and magnetic switches used in laser power sources, and the like, and for sensors of various types, such as power source sensors, directions sensors, and security sensors, and the like.
  • An amorphous alloy thin strip of thickness 15 ⁇ m was obtained by the single roll method from an alloy consisting of Fe74Cu2Mo2Si11B9N2. This amorphous alloy was then wound to form a toroidal core of external diameter 18 mm, internal diameter 12 mm, and height 4.5 mm, then heat treated for about 90 minutes at about 550°C. The crystallization of this alloy was about 575°C at a temperature rise rate of 10C o /min (measured with a rate of temperature rise of 10C o /min.
  • Fine crystal grains were present to the extent of about 85% with respect to the total area of the alloy in the magnetic core that was obtained. Of these, fine crystal grains of 50 ⁇ to 300 ⁇ represented about 90%.
  • a magnetic core was manufactured on which heat treatment was performed for about 40 minutes at about 450°C. It was found by TEM observation that fine crystal grains had not segregated in this magnetic core.
  • Fe-based soft iron alloy can be provided having excellent soft magnetic properties, having fine crystal grains in the desired alloy composition, with high saturated magnetic flux density in the high frequency region, and the required Fe-based soft magnetic materials can be easily manufactured, owing to the wide temperature range of heat treatment possible.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Soft Magnetic Materials (AREA)

Claims (10)

  1. Weiche, magnetische Legierung auf Fe-Basis mit feinen Kristallkörnern, die durch die Formel (I) definiert ist:



            Fe100-a-b-c-dMaM'bZcNd   (I)



       wobei M mindestens ein Element von den folgenden ist:
    Cu, Ag, Au, Zn, Sn, Pb, Sb, und Bi;
       wobei M' mindestens ein Element aus den folgenden ist:
    Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Co, Ni, und Al;
       Z mindestens ein Element aus den folgenden ist:
    Si, Pb und B;
       und wobei a, b, c und d in Atomprozenten ausgedrückt folgendermaßen sind:
       0,01 ≦ a ≦ 5
       0,1 ≦ b ≦ 10
       15 ≦ c ≦ 28
       0 < d ≦ 8
    und das Gebietsverhältnis der feinen Kristallkörner im Bereich von 5 bis 30 nm (50 Å bis 300 Å) mindestens 30% ist.
  2. Legierung nach Anspruch 1, wobei mindestens 80% der feinen Kristallkörner im Bereich von 5 bis 30 nm (50 Å bis 300 Å) liegen.
  3. Legierung nach Anspruch 1 oder 2, wobei a = 0,5 bis 3 Atomprozent ist.
  4. Legierung nach einem der vorhergehenden Ansprüche, wobei b = 1 bis 7 Atomprozent ist.
  5. Legierung nach Anspruch 4, wobei b = 1,5 bis 5 Atomprozent ist.
  6. Legierung nach einem der vorhergehenden Ansprüche, wobei c = 18 bis 26 Atomprozent ist.
  7. Legierung nach einem der vorhergehenden Ansprüche, wobei das Verhältnis von Si/B und/oder das Verhältnis von Si/P mehr als 1 ist.
  8. Legierung nach einem der vorhergehenden Ansprüche, wobei d kleiner als 6 Atomprozent ist.
  9. Legierung nach Anspruch 8, wobei d kleiner als 4 Atomprozent ist.
  10. Verfahren zum Behandeln einer weichen, magnetischen Legierung auf Fe-Basis nach einem der vorhergehenden Ansprüche, welches die Wärmebehandlung der Legierung über eine Zeit von einer Minute bis zu zehn Stunden bei einer Temperatur von 50°C unter der Kristallisationstemperatur bis 120°C über der Kristallisationstemperatur der Legierung umfaßt, um die feinen Kristallkörner zu trennen, wobei die Wärmebehandlung vorzugsweise über zehn Minuten bis fünf Stunden durchgeführt wird.
EP89304925A 1988-05-17 1989-05-16 Weichmagnetische Legierung auf Eisenbasis Expired - Lifetime EP0342921B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP118331/88 1988-05-17
JP63118331A JP2823203B2 (ja) 1988-05-17 1988-05-17 Ｆｅ基軟磁性合金

Publications (3)

Publication Number Publication Date
EP0342921A2 EP0342921A2 (de) 1989-11-23
EP0342921A3 EP0342921A3 (en) 1989-12-20
EP0342921B1 true EP0342921B1 (de) 1993-09-01

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ID=14734016

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EP89304925A Expired - Lifetime EP0342921B1 (de) 1988-05-17 1989-05-16 Weichmagnetische Legierung auf Eisenbasis

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EP (1) EP0342921B1 (de)
JP (1) JP2823203B2 (de)
KR (1) KR930010639B1 (de)
DE (1) DE68908768T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0800182B1 (de) * 1989-09-01 2002-11-13 Masaaki Yagi Dünner weichmagnetischer Streifen aus einer Legierung
DE69018422T2 (de) * 1989-12-28 1995-10-19 Toshiba Kawasaki Kk Auf Eisen basierende weichmagnetische Legierung, ihr Herstellungsverfahren und Magnetkern daraus.
EP0519989B1 (de) * 1990-03-16 1994-07-20 The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ferromagnetische stoffe
US5622768A (en) * 1992-01-13 1997-04-22 Kabushiki Kaishi Toshiba Magnetic core
EP0637038B1 (de) * 1993-07-30 1998-03-11 Hitachi Metals, Ltd. Magnetkern für Impulsübertrager und Impulsübertrager
JPH07268610A (ja) * 1994-03-28 1995-10-17 Alps Electric Co Ltd 軟磁性合金薄膜
DK1994375T3 (en) 2006-03-11 2016-05-30 Kracht Gmbh The volume measuring device with sensor
US20070253103A1 (en) * 2006-04-27 2007-11-01 Heraeus, Inc. Soft magnetic underlayer in magnetic media and soft magnetic alloy based sputter target
KR102465581B1 (ko) 2017-08-18 2022-11-11 삼성전기주식회사 Fe계 나노결정립 합금 및 이를 이용한 전자부품

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1471368B2 (de) * 1960-10-31 1971-11-11 E.I. Du Pont De Nemours And Co., Wilmington, Del. (V.St.A.) Verwendung eines ferromagnetischen kristallinen materials als arbeitsmittel zur energieumwandlung
DE2005371B2 (de) * 1970-02-06 1974-01-17 Fried. Krupp Gmbh, 4300 Essen Verfahren zur Herstellung weichmagnetischer Eisen-Nickel-Legierungen
JPS4992600A (de) * 1973-01-09 1974-09-04
JPS5449936A (en) * 1977-09-29 1979-04-19 Pioneer Electronic Corp High permiable* soft magnetic material and method of making same
US4881989A (en) * 1986-12-15 1989-11-21 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
JP2611994B2 (ja) * 1987-07-23 1997-05-21 日立金属株式会社 Ｆｅ基合金粉末およびその製造方法
JP2713364B2 (ja) * 1988-05-11 1998-02-16 日立金属株式会社 耐熱性に優れた超微結晶軟磁性合金
JPH05273120A (ja) * 1992-03-27 1993-10-22 Hoya Corp 偏光解析装置

Also Published As

Publication number Publication date
KR930010639B1 (ko) 1993-11-02
EP0342921A3 (en) 1989-12-20
EP0342921A2 (de) 1989-11-23
KR890017729A (ko) 1989-12-18
JP2823203B2 (ja) 1998-11-11
DE68908768D1 (de) 1993-10-07
DE68908768T2 (de) 1993-12-23
JPH01290744A (ja) 1989-11-22

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