EP0021101B1 - Amorphe weichmagnetische Legierung - Google Patents

Amorphe weichmagnetische Legierung Download PDF

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Publication number
EP0021101B1
EP0021101B1 EP80102997A EP80102997A EP0021101B1 EP 0021101 B1 EP0021101 B1 EP 0021101B1 EP 80102997 A EP80102997 A EP 80102997A EP 80102997 A EP80102997 A EP 80102997A EP 0021101 B1 EP0021101 B1 EP 0021101B1
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EP
European Patent Office
Prior art keywords
alloys
alloy
amorphous
elements
atomic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP80102997A
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German (de)
English (en)
French (fr)
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EP0021101A1 (de
Inventor
Hans-Reiner Dr. Hilzinger
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Vacuumschmelze GmbH and Co KG
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Vacuumschmelze GmbH and Co KG
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Priority to AT80102997T priority Critical patent/ATE2343T1/de
Publication of EP0021101A1 publication Critical patent/EP0021101A1/de
Application granted granted Critical
Publication of EP0021101B1 publication Critical patent/EP0021101B1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt 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

Definitions

  • the invention relates to an amorphous soft magnetic alloy containing cobalt, manganese, silicon and boron.
  • amorphous metal alloys can be produced by cooling an appropriate melt so rapidly that solidification occurs without crystallization.
  • the alloys can be obtained in the form of thin strips, the thickness of which can be, for example, a few hundredths of a mm and the width of which can be from a few mm to several cm.
  • the amorphous alloys can be distinguished from the crystalline alloys by means of X-ray diffraction measurements. In contrast to crystalline materials, which show characteristic sharp diffraction lines, the intensity in the X-ray diffraction pattern with amorphous metal alloys changes only slowly with the diffraction angle, similarly as is the case with liquids or ordinary glass.
  • the amorphous alloys can be completely amorphous or comprise a two-phase mixture of the amorphous and the crystalline state.
  • an amorphous metal alloy is understood to mean an alloy which is at least 50%, preferably at least 80%, amorphous.
  • the so-called crystallization temperature For every amorphous metal alloy there is a characteristic temperature, the so-called crystallization temperature. If the amorphous alloy is heated to or above this temperature, it changes to the crystalline state in which it remains even after cooling. In the case of heat treatments below the crystallization temperature, however, the amorphous state is retained.
  • the previously known soft magnetic amorphous alloys have a composition corresponding to the general formula M 100-t X t , where M denotes at least one of the metals Co, Ni and Fe and X denotes at least one of the so-called glass-forming elements B, Si, C and P and t between is about 5 and 40.
  • such amorphous alloys can contain, in addition to the metals M, other metals such as the transition metals Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf and Mn and that in addition to the glass-forming elements or, if appropriate, the elements Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi or Be may also be present instead of these (DE-OS 2364131.
  • amorphous soft magnetic alloys are those with small, as small as possible, magnetostriction.
  • the smallest possible saturation magnetostriction As is an essential prerequisite for good soft magnetic properties, i.e. a low coercive force and a high permeability.
  • the magnetic properties of amorphous alloys with vanishingly small magnetostriction are practically insensitive to deformation, so that such alloys can easily be wound into cores or processed into deformable shields, for example braids.
  • alloys with zero magnetostriction are not excited to vibrate under AC operating conditions, so that no energy is lost to mechanical vibrations. The core losses can therefore be very low. In addition, there is no annoying buzzing sound that often occurs with electromagnetic devices.
  • Another known group of amorphous alloys with magnetostriction values between about + 5 ⁇ 10 -6 to - 5 ⁇ 10 -6 has a composition according to the general formula (Co x Fe 1-x ) a B b C c , where x is in the range from about 0.84 to 1.0, a in the range of about 78 to 85 atomic%, b in the range of about 10 to 22 atomic%, c in the range of 0 to about 12 atomic% and b + c in the range from about 15 to 22 atomic%.
  • these alloys can contain up to about 4 atom% of at least one other transition metal, such as Ti, W, Mo, Cr, Mn, Ni and Cu, and up to about 6 atom% of at least one other metalloid Contain elements such as Si, Al and P without the desired magnetic properties are significantly deteriorated (DE-OS 2708151).
  • transition metal such as Ti, W, Mo, Cr, Mn, Ni and Cu
  • metalloid Contain elements such as Si, Al and P without the desired magnetic properties are significantly deteriorated
  • amorphous alloys consisting essentially of about 13 to 73 atomic% Co, about 5 to 50 atomic% Ni, and about 2 to 17 atomic% Fe, the total of Co, Ni and Fe is about 80 atomic percent, and the rest consists essentially of B and minor impurities.
  • These alloys can, based on the total composition, up to about 4 atom% of at least one of the elements Ti, W, Mo, Cr, Mn or Cu and up to about 6 atom% of at least one of the elements Si, Al, C and P included (DE-OS 28 35 389).
  • these alloys can additionally contain 0.5 to 6 atomic% of at least one of the elements Ti, Zr, V, Nb, Ta, Cr, Mo, W, Zn, Al, Ga, In, Ge, Sn , Pb, As, Sb and Bi contain (DE-OS 28 06 052).
  • the object of the invention is to provide a further soft magnetic alloy, in which the amount of saturation magnetostriction
  • low saturation magnetostrictions are achieved with an alloy of the composition (Co a Ni b T c Mn d Fe e ) 100-t (Si x B y M z ) t , where T at least one of the elements Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf and M are at least one of the elements P, C, AI, Ga, In, Ge, Sn, Pb, As, Sb, Bi and Be and the following relationships apply:
  • a, b, c, d, e and x, y, z mean the atomic proportions of the associated elements normalized to the total sum of the totality of the metals or metalloids and (100-t) or t the respective share of the total of the metals or metalloids in the associated brackets in the alloy in atomic%
  • the proportion of a single element in the alloy in atomic% corresponds to the product of the index of the corresponding element and the index of the associated bracket.
  • the magnetostriction constant can be reduced to zero by appropriate measurement of the manganese content.
  • the silicon results in an increase in the crystallization temperature and a decrease in the melting temperature and therefore leads to an improved manufacturability of the amorphous alloy.
  • the cooling rate is less critical in the production of the amorphous alloy.
  • the transition elements T also increase the crystallization temperature, while the Curie temperature of the alloy is also reduced with increasing metalloid content. Both result in better long-term stability of the magnetic properties of the alloy.
  • the upper limit of the metalloid content is that the Curie temperature must not drop so far that the alloy is no longer ferromagnetic at a normal temperature.
  • the manganese content at which the magnetostriction constant passes through zero becomes smaller with increasing metalloid content of the alloy and with increasing proportions of nickel and the other transition elements T.
  • ⁇ s 0
  • the relationship d 0.09 - 0.001 (t - 25 + 10b + 10c) 2 with the additional condition 0.01 ⁇ d applies approximately.
  • the alloys according to the invention already show good soft magnetic properties after production by rapid cooling from the melt, i.e. low coercivity, high permeability and low AC losses.
  • the magnetic properties, in particular of magnetic cores made from the alloy can often be further improved by an annealing treatment below the crystallization temperature.
  • Such a heat treatment can be carried out at temperatures of approximately 250 to 500 ° C., preferably 300 to 460 ° C., and may take approximately 10 minutes to 24 hours, preferably 30 minutes to 4 hours.
  • It is advantageously used in an inert atmosphere, for example vacuum, hydrogen, helium or argon, and in an external magnetic field running parallel to the tape direction, i.e. a longitudinal magnetic field, with a field strength between 1 and 200 A / cm, preferably 5 to 50 A / cm. performed.
  • the shape of the magnetization curve can be adjusted by the cooling rate after the heat treatment. Fast quenching with quenching speeds between 400 K and 10,000 K per hour gives high permeabilities even for small modulations and low losses at high frequencies of 20 kHz, for example. By slow cooling with a cooling rate of about 20 to 400 K per hour in the presence of the magnetic longitudinal field, however, particularly high maximum permeabilities and small coercive field strengths are obtained.
  • the dependence of the magnetostriction constant on the manganese content will be illustrated using the example of the alloys with the composition Co 75-d .Mn d .Si 15 B 10 .
  • the alloys listed in the following Table 1 in the form of strips approximately 0.04 mm thick and 2 mm wide were produced in a manner known per se in that the elements were melted in a quartz vessel by means of heating by induction and the melt was then melted in a Quartz vessel located opening was sprayed onto a rapidly rotating copper drum.
  • a subsequent measurement of the saturation magnetostriction constant h s gave the following values:
  • the table above also shows the saturation magnetization J, in T and the coercive field strength H e in mA / cm.
  • the values refer to the alloy in the production state without subsequent heat treatment.
  • the relationship between the saturation magnetostriction constant and the manganese content of the alloys is shown graphically in FIG. 1.
  • the zero crossing of the magnetostriction constant occurs with an alloy with about 7 atomic% manganese.
  • Tables II to IV list a number of further alloys according to the application, which were produced in accordance with the preceding example.
  • the alloys listed in Table II have particularly low magnetostriction constants ⁇ s , a relatively high saturation induction J s and, even in the state after production without heat treatment, a very low coercive force H e , measured on the stretched strip.
  • the magnitude of the magnetostriction constant is approximately 1 ⁇ 10 -6 .
  • a ring core was wound from a band of an alloy of the composition Co 48.5 Ni 20 Mn 7.5 Si 11 B 13 produced according to the first example, the permeability of which was measured in an alternating magnetic field of 50 Hz.
  • Curve 1 of FIG. 2 shows the dependency of the permeability on the maximum amplitude of the magnetic field. The permeability is given on the ordinate, the amplitude H of the magnetic field in mA / cm on the abscissa.
  • the same core was then subjected to a heat treatment at 380 ° C. under hydrogen in a longitudinal magnetic field of approximately 10 A / cm for approximately one hour and then cooled in a magnetic field at a cooling rate of approximately 100 K / h.
  • the permeabilities subsequently measured in an alternating magnetic field of 50 Hz are shown in curve 2 of FIG. 2.
  • the alloys according to the application are particularly suitable as a material for magnetic shields, sound heads and magnetic cores, in particular if the latter are to be operated at higher frequencies, for example at 20 kHz. Furthermore, because of their low magnetostriction and their very good soft magnetic properties already in the production state, the alloys according to the application are particularly suitable for applications in which the soft magnetic material has to be deformed and heat treatment is then no longer possible.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
EP80102997A 1979-06-15 1980-05-29 Amorphe weichmagnetische Legierung Expired EP0021101B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80102997T ATE2343T1 (de) 1979-06-15 1980-05-29 Amorphe weichmagnetische legierung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792924280 DE2924280A1 (de) 1979-06-15 1979-06-15 Amorphe weichmagnetische legierung
DE2924280 1979-06-15

Publications (2)

Publication Number Publication Date
EP0021101A1 EP0021101A1 (de) 1981-01-07
EP0021101B1 true EP0021101B1 (de) 1983-01-26

Family

ID=6073337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80102997A Expired EP0021101B1 (de) 1979-06-15 1980-05-29 Amorphe weichmagnetische Legierung

Country Status (6)

Country Link
US (1) US5200002A (ja)
EP (1) EP0021101B1 (ja)
JP (1) JPS563646A (ja)
AT (1) ATE2343T1 (ja)
CA (1) CA1166042A (ja)
DE (2) DE2924280A1 (ja)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7771545B2 (en) 2007-04-12 2010-08-10 General Electric Company Amorphous metal alloy having high tensile strength and electrical resistivity

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JPS5754251A (en) 1980-09-15 1982-03-31 Tdk Corp Amorphous magnetic alloy material
JPS57155339A (en) * 1981-03-20 1982-09-25 Matsushita Electric Ind Co Ltd Magnetic head and production thereof
JPS57160513A (en) * 1981-03-31 1982-10-02 Takeshi Masumoto Maunfacture of amorphous metallic fine wire
JPS57193005A (en) * 1981-05-23 1982-11-27 Tdk Corp Amorphous magnetic alloy thin belt for choke coil and magnetic core for the same
JPS5831053A (ja) * 1981-08-18 1983-02-23 Toshiba Corp 非晶質合金
JPS5884957A (ja) * 1981-11-14 1983-05-21 Matsushita Electric Ind Co Ltd 非晶質磁性合金
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DE3175475D1 (en) * 1981-11-26 1986-11-20 Allied Corp Low magnetostriction amorphous metal alloys
EP0160166A1 (en) * 1981-11-26 1985-11-06 Allied Corporation Low magnetostriction amorphous metal alloys
US4439253A (en) * 1982-03-04 1984-03-27 Allied Corporation Cobalt rich manganese containing near-zero magnetostrictive metallic glasses having high saturation induction
JPS58185743A (ja) * 1982-04-24 1983-10-29 Tdk Corp 磁気ヘッド用非晶質磁性合金薄板の製造方法
US4637843A (en) * 1982-05-06 1987-01-20 Tdk Corporation Core of a noise filter comprised of an amorphous alloy
JPS59150414A (ja) * 1982-12-23 1984-08-28 Toshiba Corp 半導体回路用リアクトル
US4553136A (en) * 1983-02-04 1985-11-12 Allied Corporation Amorphous antipilferage marker
USRE35042E (en) * 1983-02-04 1995-09-26 Allied Corporation Amorphous antipilferage marker
DE3482012D1 (de) * 1983-03-31 1990-05-23 Toshiba Kawasaki Kk Amorphe legierung fuer einen magnetkopf und magnetkopf mit einer amorphen legierung.
DE3717043A1 (de) * 1987-05-21 1988-12-15 Vacuumschmelze Gmbh Amorphe legierung fuer streifenfoermige sensorelemente
DE3900946A1 (de) * 1989-01-14 1990-07-26 Vacuumschmelze Gmbh Magnetkern fuer einen schnittstellen-uebertrager
US5395460A (en) * 1992-10-16 1995-03-07 Alliedsignal Inc. Harmonic markers made from Fe-Ni based soft magnetic alloys having nanocrystalline structure
US6232775B1 (en) * 1997-12-26 2001-05-15 Alps Electric Co., Ltd Magneto-impedance element, and azimuth sensor, autocanceler and magnetic head using the same
JP4755340B2 (ja) * 1998-09-17 2011-08-24 ヴァキュームシュメルツェ ゲーエムベーハー ウント コンパニー カーゲー 直流電流公差を有する変流器
DE19907542C2 (de) 1999-02-22 2003-07-31 Vacuumschmelze Gmbh Flacher Magnetkern
DE10134056B8 (de) * 2001-07-13 2014-05-28 Vacuumschmelze Gmbh & Co. Kg Verfahren zur Herstellung von nanokristallinen Magnetkernen sowie Vorrichtung zur Durchführung des Verfahrens
US6930581B2 (en) * 2002-02-08 2005-08-16 Metglas, Inc. Current transformer having an amorphous fe-based core
US6749695B2 (en) 2002-02-08 2004-06-15 Ronald J. Martis Fe-based amorphous metal alloy having a linear BH loop
US6613275B1 (en) * 2002-07-19 2003-09-02 Metalor Technologies Sa Non-precious dental alloy
JP4445195B2 (ja) * 2002-11-29 2010-04-07 株式会社東芝 アモルファス合金薄帯およびそれを用いた磁心
DE102005034486A1 (de) * 2005-07-20 2007-02-01 Vacuumschmelze Gmbh & Co. Kg Verfahren zur Herstellung eines weichmagnetischen Kerns für Generatoren sowie Generator mit einem derartigen Kern
US7909945B2 (en) * 2006-10-30 2011-03-22 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron-cobalt-based alloy and method for its production
US8012270B2 (en) 2007-07-27 2011-09-06 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron/cobalt/chromium-based alloy and process for manufacturing it
US9057115B2 (en) * 2007-07-27 2015-06-16 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron-cobalt-based alloy and process for manufacturing it
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Publication number Priority date Publication date Assignee Title
US7771545B2 (en) 2007-04-12 2010-08-10 General Electric Company Amorphous metal alloy having high tensile strength and electrical resistivity

Also Published As

Publication number Publication date
EP0021101A1 (de) 1981-01-07
DE2924280A1 (de) 1981-01-08
DE3061764D1 (en) 1983-03-03
US5200002A (en) 1993-04-06
JPS563646A (en) 1981-01-14
JPS6218620B2 (ja) 1987-04-23
ATE2343T1 (de) 1983-02-15
CA1166042A (en) 1984-04-24

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