EP0240600B1 - Alliages métalliques vitreux à caractéristiques perminvar - Google Patents

Alliages métalliques vitreux à caractéristiques perminvar Download PDF

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Publication number
EP0240600B1
EP0240600B1 EP19860115434 EP86115434A EP0240600B1 EP 0240600 B1 EP0240600 B1 EP 0240600B1 EP 19860115434 EP19860115434 EP 19860115434 EP 86115434 A EP86115434 A EP 86115434A EP 0240600 B1 EP0240600 B1 EP 0240600B1
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EP
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Prior art keywords
alloys
magnetic
perminvar
formula
glassy
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Expired
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EP19860115434
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German (de)
English (en)
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EP0240600A1 (fr
Inventor
Ryusuke C/O Allied Corporation Hasegawa
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Honeywell International Inc
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AlliedSignal Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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
    • H01F1/15316—Amorphous metallic alloys, e.g. glassy metals based on Co

Definitions

  • This invention relates to glassy metal alloys with Perminvar characteristics that is constant permeabilities at low magnetic field excitations and constricted hysteresis loops. More particularly, this invention provides glassy metal alloys with highly non-linear magnetic properties at low magnetic excitation levels.
  • the magnetic response namely magnetic induction caused by magnetic excitation, of a typical ferromagnet
  • This loop usually does not allow a relatively constant permeability near the zero-excitation point.
  • Perminvar alloys were developed [see, for example, R. M. Bozorth, Ferromagnetism (Van Nostrand, Co., Inc., New York, 1951) p. 166-180]. These alloys are usually based on crystalline iron-cobalt-nickel system. Typical compositions (weight percent) include 20%Fe-60%Co-20%Ni (20-60 Perminvar) and 30%Fe-25%Co-45%Ni (45-45 Perminvar).
  • Saturation magnetostriction ⁇ s is related to the fractional change in length ⁇ l/l that occurs in a magnetic material on going from the demagnetized to the saturated, ferromagnetic state.
  • the value of magnetostriction a dimensionless quantity, is often given in units of microstrains (i.e., a microstrain is a fractional change in length of one part per million).
  • Ferromagnetic alloys of low magnetostriction are desirable for several interrelated reasons:
  • Zero magnetostrictive alloys based on the binaries but with small additions of other elements such as molybdenum, copper or aluminum to provide specific property changes. These include, for example, 4% Mo, 79% Ni, 17% Fe (sold under the designation Moly Permalloy) for increased resistivity and permeability; permalloy plus varying amounts of copper (sold under the designation Mumetal) for magnetic softness and improved ductility; and 85 wt. % Fe, 9 wt. % Si, 6 wt. % Al (sold under the designation Sendust) for zero anisotropy.
  • the alloys included in category (1) are the most widely used of the three classes listed above because they combine zero magnetostriction with low anisotropy and are, therefore, extremely soft magnetically; that is they have a low coercivity, a high permeability and a low core loss. These permalloys are also relatively soft mechanically and their excellent magnetic properties, achieved by high temperature (above 1000°C) anneal, tend to be degraded by relatively mild mechanical shock.
  • Category (2) alloys such as those based on Co90Fe10 have a much higher saturation induction (B s about 1.9 Tesla) than the permalloys. However, they also have a strong negative magnetocrystalline anisotropy, which prevents them from being good soft magnetic materials. For example, the initial permeability of Co90Fe10 is only about 100 to 200.
  • Category (3) alloys such as Fe-6 wt% Si and the related ternary alloy Sendust (mentioned above) also show higher saturation inductions (B s about 1.8 Tesla and 1.1 Tesla, respectively) than the permalloys.
  • these alloys are extremely brittle and have, therefore, found limited use in powder form only.
  • compositional dependence of the magnetostriction is very strong in these materials, making difficult precise tayloring of the alloy composition to achieve near-zero maganetostriction.
  • glassy metal alloys of zero magnetostriction Such alloys might be found near the compositions listed above. Because of the presence of metalloids which tend to reduce the magnetization by dilution and electronic hybridization, however, glassy metal alloys based on the 80 nickel permalloys are either non-magnetic at room temperature or have unacceptably low saturation inductions.
  • the glassy alloy Fe40Ni40P14B6 (the subscripts are in atom percent) has a saturation induction of about 0.8 Tesla, while the glassy alloy Ni49Fe29P14B6Si2 has a saturation induction of about 0.46 Tesla and the glassy alloy Ni80P20 is non-magnetic.
  • No glassy metal alloys having a saturation magnetostriction approximately equal to zero have yet been found near the iron-rich Sendust composition.
  • a number of near-zero magnetostrictive glassy metal alloys based on the Co-Fe crystalline alloy mentioned above in (2) have been reported in the literature. These are, for example, Co72Fe3P16B6Al3 (AIP Conference Proceedings, No. 24, pp.
  • the crystalline materials mentioned-above have to be baked for a long time at a given temperature.
  • the heat-treatment is performed at 425°C for 24 hours.
  • EP-A-84138 discloses glassy metal alloys of near zero magnetostriction having the formula Co a Fe b Ni c Mo d B e Si f , where "a" to "f" are in atom percent, a is from 58 to 70, b is from 2 to 75, c is from 0 to 8, d is from 1 to 2, e is from 11 to 15 and f is from 9 to 14, the sum of a, b and c being from 72 to 76 and the sum of e and f being from 23 to 26. There is no description of how to obtain therefrom any alloy having Perminvar characteristics.
  • a magnetic alloy that is at least 70% glassy, having the formula Co a Fe b Ni c M d B e Si f , where M is at least one of Cr, Mo, Mn and Nb, "a" - “f” are in atom percent and the sums of "a” - “f” equals 100, “a” is from 66 to 71, “b” is from 2.5 to 4.5, “c” is from 0 to 3, “d” is from 0 to 4, “e” is from 6 to 24 and “f” is from 0 to 19, with the provisos that the sum of "a", “b” and “c” is from 71 to 76 and the sum of "e” and “f” is from 25 to 27 and up to 4 atom percent of Si may be replaced by C, Al and Ge, said alloy having a value of magnetostriction between - 1x10 ⁇ 6 and + 1x10 ⁇ 6, said alloy having Perminvar characteristics of a relatively constant permeability at low magnetic excitation
  • T a and t a should exclude the case that ⁇ T c-a ⁇ 50°C and t a 15 minutes because such combination sometimes results in crystallization of the glassy alloy.
  • the metal M in the alloys may be replaced by at least one other element such as vanadium, tungsten, tantalum, titanium, zirconium and hafnium, and up to 4 atom percent of Si may be replaced by carbon, aluminum or germanium without significantly degrading the desirable magnetic properties of these alloys.
  • Examples of near-zero magnetostrictive glassy metal alloys for heat treatment in accordance with the invention include Co 70.5 Fe 4.5 B15Si10, Co 69.0 Fe 4.1 Ni 1.4 Mo 1.5 B12Si12, Co 65.7 Fe 4.4 Ni 2.9 Mo2B11Si14, Co 69.2 Fe 3.8 Mo2B8Si17, Co 67.5 Fe 4.5 Ni 3.0 B8Si17, Co 70.9 Fe 4.1 B8Si17, Co 69.9 Fe 4.1 Mn 1.0 B8Si17, Co 69.0 Fe 4.0 Mn2B8Si17, Co 68.0 Fe 4.0 Mn3B8Si17, Co 67.1 Fe 3.9 Mn4B8Si17, Co 68.0 Fe 4.0 Mn2Cr1B8Si17, Co 69.0 Fe 4.0 Cr2B8Si17, Co 69.0 Fe 4.0 Nb2B8Si17, Co 68.2 Fe 3.8 Mn1B12Si15, Co 67.7
  • the constricted B-H loops of Figs 1B and 1C are characteristic of the materials with Perminvar-like properties, whereas the B-H loop of Fig. 1A corresponds to that of a typical soft ferromagnet.
  • the choice of the heat-treatment temperature T a is very important in obtaining the Perminvar characteristics in the glassy alloys. Table II summarizes the heat-treatment conditions for some of these alloys and some of the resultant magnetic properties.
  • the glassy alloys of the invention are conveniently prepared by techniques readily available elsewhere; see e.g. US Patent No. 3,845,805 and No. 3,856,513.
  • the glassy alloys, in the form of continuous ribbon or wire are rapidly quenched from a melt of the desired composition at a rate of at least about 105 K/sec.
  • these alloys exhibit high permeabilities and low core loss at high frequencies.
  • the glassy alloys listed in Tables I-III were rapidly quenched (about 106 K/sec) from the melt following the techniques taught by Chen and Polk in U.S. Patent 3,856,513.
  • the resulting ribbons typically 25 to 30 ⁇ m thick and 0.5 to 2.5 cm wide, were determined to be free of significant crystallinity by X-ray diffractometry (using CuK radiation) and scanning calorimetry. Ribbons of the glassy metal alloys were strong, shiny, hard and ductile.
  • Continuous ribbons of the glassy metal alloys prepared in accordance with the procedure described in Example I were wound onto bobbins (3.8 cm O.D.) to form closed-magnetic-path toroidal samples. Each sample contained from 1 to 3 g of ribbon. Insulated primary and secondary windings (numbering at least 10 each) were applied to the toroids. These samples were used to obtain hysteresis loops (coercivity and remanence) and initial permeability with a commercial curve tracer and core loss (IEEE Standard 106-1972).
  • the ferromagnetic Curie temperature ( ⁇ f ) was measured by inductance method and also monitored by differential scanning calorimetry, which was used primarily to determine the crystallization temperatures.
  • Magnetostriction measurements employed metallic strain gauges (BLH Electronics), which were bonded (Eastman - 910 Cement) between two short lengths of ribbon. The ribbon axis and gauge axis were parallel. The magnetostriction was determined as a function of applied field from the longitudinal strain in the parallel ( ⁇ l/ l) and perpendicular ( ⁇ l/l) in-plain fields, according to the formula

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
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Claims (7)

  1. Alliage magnétique qui est au moins vitreux à 70 %, répondant à la formule CoaFebNicMdBeSif, dans laquelle M est au moins l'un des éléments Cr, Mo, Mn et Nb, "a" - "f"- sont des atomes % et la somme de "a" - "f" est égale à 100, "a" est compris entre 66 et 71, "b" est compris entre 2,5 et 4,5, "c" est compris entre 0 et 3, "d" est compris entre 0 et 4, "e" est compris entre 6 et 24 et "f" est compris entre 0 et 19, dans la mesure où la somme de "a", "b" et "c" est comprise entre 71 et 76 et la somme de "e" et "f" est comprise entre 25 et 27 et jusqu'à 4 atomes % de Si peuvent être remplacés par C, Al ou Ge, ledit alliage ayant une valeur de la magnétostriction comprise entre - 1x10⁻⁶ et + 1x10⁻⁶, ledit alliage ayant les caractéristiques d'un Perminvar de perméabilité relativement constante à une faible excitation magnétique et une courbe d'hystérésis rétrécie à la suite de la soumission à un traitement thermique par chauffage à une température comprise entre 50 et 110°C au-dessous de sa première température de cristallisation pendant une durée comprise entre 15 et 180 minutes et ensuite par refroidissement à une cadence inférieure à environ - 60°C/mn.
  2. Alliage magnétique selon la revendication 1, ayant la formule Co70,5Fe4,5B₁₅Si₁₀.
  3. Alliage magnétique selon la revendication 1, ayant la formule Co65,7Fe4,4Ni2,9Mo₂B₁₁Si₁₄.
  4. Alliage magnétique selon la revendication 1, ayant la formule Co68,2Fe3,8Mn₁B₁₂Si₁₅.
  5. Alliage magnétique selon la revendication 1, ayant la formule Co67,7Fe3,3Mn₂B₁₂Si₁₅.
  6. Alliage magnétique selon la revendication 1, ayant la formule Co67,8Fe4,2Mo₁B₁₂Si₁₅.
  7. Alliage magnétique selon la revendication 1, ayant une formule choisie parmi :
    Co67,8Fe4,2Cr₁B₁₂Si₁₅, Co69,2Fe3,8Mo₂B₈Si₁₇, Co67,5Fe4,5Ni3,0B₈Si₁₇, Co70,9Fe4,1B₈Si₁₇, Co69,9Fe4,1Mn1,0B₈Si₁₇, Co69,0Fe4,0Mn₂B₈Si₁₇, Co68,0Fe4,0Mn₃B₈Si₁₇, Co67,1Fe3,9Mn₄B₈Si₁₇, Co69,0Fe4,0Cr₂B₈Si₁₇, Co68,0Fe4,0Mn₂Cr₁B₈Si₁₇, Co69,0Fe4,0Nb₂B₈Si₁₇, Co67,0Fe4,0Cr₂B₁₂Si₁₅.
EP19860115434 1986-01-08 1986-11-07 Alliages métalliques vitreux à caractéristiques perminvar Expired EP0240600B1 (fr)

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US81719386A 1986-01-08 1986-01-08
US817193 1986-01-08

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EP0240600A1 EP0240600A1 (fr) 1987-10-14
EP0240600B1 true EP0240600B1 (fr) 1992-05-13

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JP (2) JP2552274B2 (fr)
CA (1) CA1317484C (fr)
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US5003291A (en) * 1988-12-27 1991-03-26 Strom Olsen John O Ferromagnetic fibers having use in electronical article surveillance and method of making same
US5015992A (en) * 1989-06-29 1991-05-14 Pitney Bowes Inc. Cobalt-niobium amorphous ferromagnetic alloys
US6457464B1 (en) 1996-04-29 2002-10-01 Honeywell International Inc. High pulse rate spark ignition system
US5844462A (en) * 1996-04-29 1998-12-01 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
US5923236A (en) * 1996-04-29 1999-07-13 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition system
EP0896726A1 (fr) * 1996-04-29 1999-02-17 AlliedSignal Inc. Ensemble bobine/noyau magnetiques pour systeme d'allumage commande
CN1292926A (zh) 1997-09-18 2001-04-25 联合讯号公司 高脉冲重复频率点火源
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
US6580347B1 (en) 1998-11-13 2003-06-17 Vacuumschmelze Gmbh Magnetic core that is suitable for use in a current transformer, method for the production of a magnetic core and current transformer with a magnetic core
GB2374084A (en) * 2001-04-03 2002-10-09 Fourwinds Group Inc Alloys having bistable magnetic behaviour
JP5700328B2 (ja) * 2010-04-26 2015-04-15 セイコーエプソン株式会社 Ｃｏ基金属ガラス合金、磁心、電磁変換機および時計
ES2524733B2 (es) * 2014-07-25 2015-03-31 Universidad Complutense De Madrid Sensor inalámbrico para detectar presión
WO2018128149A1 (fr) * 2017-01-05 2018-07-12 Tdk株式会社 Noyau et réacteur, limiteur de courant, actionneur électromagnétique et moteur utilisant ledit noyau

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SE7511398L (sv) * 1974-10-21 1976-04-22 Western Electric Co Magnetisk anordning
US4188211A (en) * 1977-02-18 1980-02-12 Tdk Electronics Company, Limited Thermally stable amorphous magnetic alloy
JPS5934780B2 (ja) * 1977-12-16 1984-08-24 松下電器産業株式会社 非晶質磁性合金薄板の熱処理法
JPS5825449A (ja) * 1981-08-05 1983-02-15 Toshiba Corp 磁気ヘツド用非晶質磁性合金
DE3275492D1 (en) * 1982-01-18 1987-04-02 Allied Corp Near-zero magnetostrictive glassy metal alloys with high magnetic and thermal stability
JPS59179751A (ja) * 1983-03-31 1984-10-12 Toshiba Corp 可飽和リアクトル用非晶質合金

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JP2907271B2 (ja) 1999-06-21
JPS62170446A (ja) 1987-07-27
EP0240600A1 (fr) 1987-10-14
JPH08188858A (ja) 1996-07-23
DE3685326D1 (de) 1992-06-17
CA1317484C (fr) 1993-05-11
JP2552274B2 (ja) 1996-11-06

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