EP0240600A1 - Glasartige Legierungen mit Perminvar-Eigenschaften - Google Patents

Glasartige Legierungen mit Perminvar-Eigenschaften Download PDF

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Publication number
EP0240600A1
EP0240600A1 EP19860115434 EP86115434A EP0240600A1 EP 0240600 A1 EP0240600 A1 EP 0240600A1 EP 19860115434 EP19860115434 EP 19860115434 EP 86115434 A EP86115434 A EP 86115434A EP 0240600 A1 EP0240600 A1 EP 0240600A1
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EP
European Patent Office
Prior art keywords
ranges
alloy
glassy
alloys
magnetic
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EP19860115434
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English (en)
French (fr)
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EP0240600B1 (de
Inventor
Ryusuke C/O Allied Corporation Hasegawa
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Honeywell International Inc
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Allied Corp
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 as 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 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 C0 90 Fe lo 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 Co 90 Fe 10 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 Fe 40 Ni 40 P 14 B 6 (the subscripts are in atom percent) has a saturation induction of about 0.8 Tesla, while the glassy alloy Ni 49 Fe 29 P 14 B 6 Si 2 has a saturation induction of about 0.46 Tesla and the glassy alloy N i 80P20 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, Co 72 Fe 3 P 16 B 6 Al 3 (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-rtreatment is performed at 425°C for 24 hours.
  • a magnetic alloy that is at least 70% glassy and which has a low magnetostriction and Perminvar characteristics of relatively constant permeability at low magnetic field excitations and a constricted hysteresis loop in addition to excellent soft magnetic properties.
  • the glassy alloy has a value of magnetostriction ranging from about - 1 ⁇ 10 -6 to + 1x10 -6 , a saturation induction ranging from about 0.5 to 1 Tesla, a Curie temperature ranging from about 200 to 450°C and a first crystallization temperature ranging from about 440 to 570°C.
  • the glassy alloy is heat-treated by heating it to a temperature between about 50 and 110°C below its first crystallization temperature for a time period ranging from 15 to 180 min., and then cooling the alloy at a rate slower than about - 60°C/min.
  • the choice of 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 of the invention may be replaced by at least one other element such as vanadium, tungsten, tantalum, titanium, zirconium and hafnium, and up to about 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 of the invention include Co 70.5 Fe 4.5 B 15 Si 10 , Co 69.0 Fe 4.1 Ni 1.4 Mo 1.5 B 12 Si 12 , Co 65.7 Fe 4.4 Ni 2.9 Mo 2 B 11 Si 14 , Co 69.2 Fe 3.8 Mo 2 B 8 Si 17 , Co 67.5 Fe 4.5 Ni 3.0 B 8 Si 17 , Co 70.9 Fe 4.1 B 8 Si 17 , Co 69.9 Fe 4.1 Mn 1.0 B 8 Si 17 , Co 69.0 Fe 4.0 Mn 2 B 8 Si 17 , Co 68.0 Fe 4.0 Mn 3 B 8 Si 17 , Co 67.1 Fe 3.9 Mn 4 B 8 Si 17 , Co 68.0 Fe 4.0 Mn 2 Cr 1 B 8 Si 17 , Co 69.0 Fe 4.0 Cr 2 B 8 Si 17 , Co 69.0 Fe 4.0 Nb 2 B 8 Si 17 , Co 68.2 Fe 3.8 Mn 1 B 12 Si 15 , Co 67.7 Fe 3.3 Mn 2 B
  • 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 glassy alloys of the invention are conveniently prepared by techniques readily available elsewhere; see e.g. US Patent No. 3,845,805 issued November 5, 1974 and No. 3,856,513 issued December 24, 1974.
  • the glassy alloys, in the form of continuous ribbon, wire, etc. are rapidly quenched from a melt of the desired composition at a rate of at least about 10 5 K/sec.
  • these alloys exhibit high permeabilities and low core loss at high frequencies.
  • T a and t a are heat-treatment temperature and time. Cooling after the heat-treatment is about -5°C/min., unless otherwise stated.
  • the glassy alloys listed in Tables I-III were rapidly quenched (about 10 6 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Soft Magnetic Materials (AREA)
EP19860115434 1986-01-08 1986-11-07 Glasartige Legierungen mit Perminvar-Eigenschaften Expired EP0240600B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US81719386A 1986-01-08 1986-01-08
US817193 1986-01-08

Publications (2)

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

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EP19860115434 Expired EP0240600B1 (de) 1986-01-08 1986-11-07 Glasartige Legierungen mit Perminvar-Eigenschaften

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EP (1) EP0240600B1 (de)
JP (2) JP2552274B2 (de)
CA (1) CA1317484C (de)
DE (1) DE3685326D1 (de)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2641104A1 (de) * 1988-12-27 1990-06-29 Pitney Bowes Inc
GB2233346A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
WO1997041574A1 (en) * 1996-04-29 1997-11-06 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO1997041576A1 (en) * 1996-04-29 1997-11-06 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO1998049697A1 (en) * 1997-04-29 1998-11-05 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO2000017897A1 (de) * 1998-09-17 2000-03-30 Vacuumschmelze Gmbh Stromwandler mit gleichstromtoleranz
WO2000030131A1 (de) * 1998-11-13 2000-05-25 Vacuumschmelze Gmbh Magnetkern, der zum einsatz in einem stromwandler geeignet ist, verfahren zur herstellung eines magnetkerns und stromwandler mit einem magnetkern
US6457464B1 (en) 1996-04-29 2002-10-01 Honeywell International Inc. High pulse rate spark ignition system
GB2374084A (en) * 2001-04-03 2002-10-09 Fourwinds Group Inc Alloys having bistable magnetic behaviour
US6535096B1 (en) 1997-09-18 2003-03-18 Honeywell International Inc. High pulse rate ignition system
ES2524733A1 (es) * 2014-07-25 2014-12-11 Universidad Complutense De Madrid Sensor inalámbrico para detectar presión.

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP7127545B2 (ja) * 2017-01-05 2022-08-30 Tdk株式会社 電磁アクチュエータ

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4188211A (en) * 1977-02-18 1980-02-12 Tdk Electronics Company, Limited Thermally stable amorphous magnetic alloy
US4288260A (en) * 1977-12-16 1981-09-08 Matsushita Electric Industrial Co. Ltd. Method of heat treatments of amorphous alloy ribbons
EP0084138A2 (de) * 1982-01-18 1983-07-27 Allied Corporation Metallegierungen mit Glasstruktur, einer Magnetostriktion in der Nähe von Null und hoher thermischer und magnetischer Stabilität

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE7511398L (sv) * 1974-10-21 1976-04-22 Western Electric Co Magnetisk anordning
JPS5825449A (ja) * 1981-08-05 1983-02-15 Toshiba Corp 磁気ヘツド用非晶質磁性合金
JPS59179751A (ja) * 1983-03-31 1984-10-12 Toshiba Corp 可飽和リアクトル用非晶質合金

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4188211A (en) * 1977-02-18 1980-02-12 Tdk Electronics Company, Limited Thermally stable amorphous magnetic alloy
US4288260A (en) * 1977-12-16 1981-09-08 Matsushita Electric Industrial Co. Ltd. Method of heat treatments of amorphous alloy ribbons
EP0084138A2 (de) * 1982-01-18 1983-07-27 Allied Corporation Metallegierungen mit Glasstruktur, einer Magnetostriktion in der Nähe von Null und hoher thermischer und magnetischer Stabilität

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
APPLIED PHYSICS LETTERS, vol. 36, no. 4, February 1980 KOICHI ASO "Observation of magnetic hysteresis loop of the perminvar type in worked Co-based amorphos alloys" pages 339-341 abstract *
ELEKTROTECHNIK UND MASCHINENBAU, 97. Jahrgang, Heft 9, September 1980 RICHARD HAFERL "Glasartige Metalle - Eigenschaften und Anwendungen" pages 378-385 page 383, lines 16-40 *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2641104A1 (de) * 1988-12-27 1990-06-29 Pitney Bowes Inc
GB2233346A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2264716A (en) * 1989-06-29 1993-09-08 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2233346B (en) * 1989-06-29 1993-12-22 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2264716B (en) * 1989-06-29 1994-02-23 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
US5923236A (en) * 1996-04-29 1999-07-13 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition system
US6457464B1 (en) 1996-04-29 2002-10-01 Honeywell International Inc. High pulse rate spark ignition system
WO1997041575A1 (en) * 1996-04-29 1997-11-06 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
US5844462A (en) * 1996-04-29 1998-12-01 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO1997041574A1 (en) * 1996-04-29 1997-11-06 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO1997041576A1 (en) * 1996-04-29 1997-11-06 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
WO1998049697A1 (en) * 1997-04-29 1998-11-05 Alliedsignal Inc. Magnetic core-coil assembly for spark ignition systems
US6535096B1 (en) 1997-09-18 2003-03-18 Honeywell International Inc. High pulse rate ignition system
WO2000017897A1 (de) * 1998-09-17 2000-03-30 Vacuumschmelze Gmbh Stromwandler mit gleichstromtoleranz
US6563411B1 (en) 1998-09-17 2003-05-13 Vacuumschmelze Gmbh Current transformer with direct current tolerance
WO2000030131A1 (de) * 1998-11-13 2000-05-25 Vacuumschmelze Gmbh Magnetkern, der zum einsatz in einem stromwandler geeignet ist, verfahren zur herstellung eines magnetkerns und stromwandler mit einem magnetkern
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
ES2524733A1 (es) * 2014-07-25 2014-12-11 Universidad Complutense De Madrid Sensor inalámbrico para detectar presión.
WO2016012636A1 (es) * 2014-07-25 2016-01-28 Universidad Complutense De Madrid Sensor inalámbrico para detectar presión.

Also Published As

Publication number Publication date
EP0240600B1 (de) 1992-05-13
JP2552274B2 (ja) 1996-11-06
JP2907271B2 (ja) 1999-06-21
JPS62170446A (ja) 1987-07-27
JPH08188858A (ja) 1996-07-23
CA1317484C (en) 1993-05-11
DE3685326D1 (de) 1992-06-17

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