EP0021101A1 - Amorphous soft magnetic alloy - Google Patents

Amorphous soft magnetic alloy Download PDF

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EP0021101A1
EP0021101A1 EP80102997A EP80102997A EP0021101A1 EP 0021101 A1 EP0021101 A1 EP 0021101A1 EP 80102997 A EP80102997 A EP 80102997A EP 80102997 A EP80102997 A EP 80102997A EP 0021101 A1 EP0021101 A1 EP 0021101A1
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Prior art keywords
alloys
alloy
soft magnetic
elements
amorphous
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German (de)
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EP0021101B1 (en
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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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    • 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, In the case of amorphous metal alloys, the intensity in the X-ray diffraction pattern 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 means an alloy that is at least 50%, preferably at least 80%, amorphous.
  • the so-called crystallization temperature For every amoapre 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 23 64 131, DE-OS 25 53 003, DE-OS 26 05 615, JP-OS 51-73923).
  • 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 23 64 131, DE-OS 25 53 003, DE-OS 26 05 615, JP-OS 51-73923).
  • amorphous soft magnetic alloys are those with small, as small as possible smaller, magnetostriction.
  • the smallest possible saturation magnetostriction ⁇ s is an essential prerequisite for good soft magnetic properties, ie 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 (Go 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 F, without the desired magnetic properties are significantly deteriorated (DE-OS 27 08 151).
  • at least one other transition metal such as Ti, W, Mo, Cr, Mn, Ni and Cu
  • at least one other metalloid Contain elements such as Si, Al and F
  • 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 remainder 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 Ef and M are at least one of the elements P, C, Al, 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, standardized to the total sum 1, of the totality of the metals or metalloids and (100-t) or t the respective proportion of the total of the metals or metalloids in the associated brackets in the alloy in atomic%.
  • the proportion of an individual 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 has 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 in the preparation of the amorphous alloy is less critical.
  • 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 as the alloy's metalloid content increases 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, for example, 20 kHz. By contrast, slow cooling at a cooling rate of about 20 to 400 K per hour in the presence of the longitudinal magnetic field gives particularly high maximum permeabilities and small coercive field strengths.
  • the table above also shows the saturation magnetization J s in T and the coercive field strength H c in specified.
  • 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, and even in the state after production without heat treatment, a very low coercive force H c , measured on the stretched strip.
  • the magnitude of the magnetostriction constant is approximately 1 ⁇ 10 -6 . in terms of amount
  • 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 on the ordinate, the amplitude H of the magnetic field in indicated on the abscissa.
  • the same core was then subjected to a heat treatment at 380 ° C. for about one hour under hydrogen in a magnetic longitudinal field of about 10 A / cm and then cooled in a magnetic field at a cooling rate of about 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 subsequently heat treatment is no longer possible.

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Abstract

1. An amorphous soft-magnetic alloy containing cobalt, manganese, silicon and boron, characterized by the composition see diagramm : EP0021101,P6,F1 where T is at least one of the elements Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf, and M is at least one of the elements P, C, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi and Be, and the following relationships are valid : see diagramm : EP0021101,P6,F2

Description

Die Erfindung betrifft eine amorphe weichmagnetische Legierung, die Kobalt, Mangan, Silizium und Bor enthält.The invention relates to an amorphous soft magnetic alloy containing cobalt, manganese, silicon and boron.

Amorphe Metallegierungen lassen sich bekanntlich dadurch herstellen, daß man eine entsprechende Schmelze so rasch abkühlt, daß ein Erstarren ohne Kristallisation eintritt. Die Legierungen können dabei gleich bei ihrer Entstehung in Form dünner Bänder gewonnen werden, deren Dicke beispielsweise einige hunderstel mm und deren Breite einige mm bis mehrere cm betragen kann.As is known, 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.

Von den kristallinen Legierungen lassen sich die amorphen Legierungen durch Röntgenbeugungsmessungen unterscheiden. Im Gegensatz zu kristallinen Materialien, die charakteristische scharfe Beugungslinien zeigen, verändert sich bei amorphen Metallegierungen die Intensität im Röntgenbeugungsbild nur langsam mit dem Beugungswinkel, ähnlich wie dies auch bei Flüssigkeiten oder gewöhnlichem Glas der Fall ist.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, In the case of amorphous metal alloys, the intensity in the X-ray diffraction pattern changes only slowly with the diffraction angle, similarly as is the case with liquids or ordinary glass.

Je nach den Herstellungsbedingungen können die amorphen Legierungen vollständig amorph sein oder ein zweiphasiges Gemisch des amorphen und des kristallinen Zustandes umfassen. Im allgemeinen versteht man unter einer amorphen Metallegierung eine Legierung, die zu wenigstens 50 %, vorzugsweise zu wenigstens 80 %, amorph ist.Depending on the manufacturing conditions, the amorphous alloys can be completely amorphous or comprise a two-phase mixture of the amorphous and the crystalline state. In general, an amorphous metal alloy means an alloy that is at least 50%, preferably at least 80%, amorphous.

Für jede amoapre Metallegierung gibt es eine charakteristische Temperatur, die sogenannte Kristallisationstemperatur. Erhitzt man die amorphe Legierung auf oder über diese Temperatur, so geht sie in den kristallinen Zustand über, in dem sie auch nach Abkühlung verbleibt. Bei Wärmebehandlungen unterhalb der Kristallisationstemperatur bleibt dagegen der amorphe Zustand erhalten.For every amoapre 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.

Die bislang bekannten weichmagnetischen amorphen Legierungen haben eine der allgemeinen Formel M100-tXt entsprechende Zusammensetzung, wobei M wenigstens eines der Metalle Co, Ni und Fe und X wenigstens eines der sogenannten glasbildenden Elemente B, Si, C und P bedeutet und t zwischen etwa 5 und 40 liegt. Ferner ist es bekannt, daß derartige amorphe Legierungen zusätzlich zu den Metallen M auch noch weitere Metalle, wie die Übergangsmetalle Cr, Mo, W, V, Nb, Ta, Ti, Zr, Hf und Mn enthalten können und daß zusätzlich zu den glasbildenden Elementen oder gegebenenfalls auch anstelle von diesen beispielsweise die Elemente Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi oder Be vorhanden sein können (DE-OS 23 64 131, DE-OS 25 53 003, DE-OS 26 05 615, JP-OS 51-73923).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. Furthermore, it is known that 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 23 64 131, DE-OS 25 53 003, DE-OS 26 05 615, JP-OS 51-73923).

Von besonderem Interesse unter den amorphen weichmagnetischen Legierungen sind solche mit kleiner, möglichst verschwindend kleiner,Nagnetostriktion. Eine möglichst kleine Sättigungsmagnetostriktion λs ist nämlich eine wesentliche Voraussetzung für gute weichmagnetische Eigenschaften, d.h. eine niedrige Koerzitivkraft und eine hohe Permeabilität. Ferner sind die magnetischen Eigenschaften von amorphen Legierungen mit verschwindend kleiner Magnetostriktion praktisch unempfindlich gegen Verformungen, so daß sich solche Legierungen leicht zu Kernen wickeln oder zu verformbaren Abschirmungen, beispielsweise Geflechten, verarbeiten lassen. Weiterhin werden Legierungen mit der Magnetostriktion Null unter Wechselstrombetriebsbedingungen nicht zu Schwingungen angeregt, so daß keine Energie an mechanische Schwingungen verlorengeht. Die Kernverluste können daher sehr gering sein. Außerdem entfällt der sonst häufig bei elektromagnetischen Einrichtungen auftretende störende Summton.Of particular interest among the amorphous soft magnetic alloys are those with small, as small as possible smaller, magnetostriction. The smallest possible saturation magnetostriction λ s is an essential prerequisite for good soft magnetic properties, ie a low coercive force and a high permeability. Furthermore, 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. Furthermore, 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.

Innerhalb des vorgenannten allgemeinen Zusammensetzungsbereichs der weichmagnetischen amorphen Legierungen sind auch bereits verschiedene Gruppen von Legierungen mit besonders niedriger Magnetostriktion bekannt geworden. Eine Gruppe solcher Legierungenhat die Zusammensetzung (CoaFebTc)yX1-y, wobei T wenigstens eines der Elemente Ni, Cr, Mn, V, Ti, Mo, W, Nb, Zr, Pd, Pt, Cu, Ag und Au und X wenigstens eines der Elemente P, Si, B, C, As, Ge, Al, Ga, In, Sb, Bi und Sn bedeutet und die Bedingungen y = 0,7 bis 0,9; a = 0,7 bis 0,97; b = 0,03 bis 0,25 und a + b + c = 1 gelten (DE-OS 25 46 676).Various groups of alloys with particularly low magnetostriction have also become known within the abovementioned general compositional range of the soft magnetic amorphous alloys. A group of such alloys has the composition (Co a Fe b T c ) y X 1-y , where T is at least one of the elements Ni, Cr, Mn, V, Ti, Mo, W, Nb, Zr, Pd, Pt, Cu, Ag and Au and X mean at least one of the elements P, Si, B, C, As, Ge, Al, Ga, In, Sb, Bi and Sn and the conditions y = 0.7 to 0.9; a = 0.7 to 0.97; b = 0.03 to 0.25 and a + b + c = 1 apply (DE-OS 25 46 676).

Eine weitere bekannte Gruppe von amorphen Legierungen mit Magnetostriktionswerten zwischen etwa +5·10-6 bis -5·10-6 hat eine Zusammensetzung entsprechend der allgemeinen Formel (GoxFe1-x)aBbCc, wobei x im Bereich von etwa 0,84 bis 1,0, a im Bereich von etwa 78 bis 85 Atom-%, b im Bereich von etwa 10 bis 22 Atom-%, c im Bereich von 0 bis etwa 12 Atom-% und b + c im Bereich von etwa 15 bis 22 Atom-% liegen. Außerdem können diese Legierungen, bezogen auf die Gesamtzusammensetzung, noch bis zu etwa 4 Atom-% wenigstens eines anderen Übergangsmetalles, wie Ti, W, Mo, Cr, Mn, Ni und Cu, und bis zu etwa 6 Atom-% wenigstens eines anderen metalloiden Elementes, wie Si, Al und F enthalten, ohne daß die erwünschten magnetischen Eigenschaften wesentlich verschlechtert werden (DE-OS 27 08 151).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 (Go 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%. In addition, based on the total composition, 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 F, without the desired magnetic properties are significantly deteriorated (DE-OS 27 08 151).

Ferner finden sich niedrige Sättigungsmagnetostriktionen bei amorphen Legierungen, die im wesentlichen aus etwa 13 bis 73 Atom-% Co, etwa 5 bis 50 Atom-% Ni, und etwa 2 bis 17 Atom-% Fe bestehen, wobei die Gesamtheit von Co, Ni und Fe etwa 80 Atom-% beträgt, und der Rest im wesentlichen aus B und geringfügigen Verunreinigungen besteht. Auch diese Legierungen können, bezogen auf die Gesamtzusammensetzung, bis zu etwa 4 Atom-% wenigstens eines der Elemente Ti, W, Mo,Cr, Mn oder Cu und bis zu etwa 6 Atom-% wenigstens eines der Elemente Si, Al, C und P enthalten (DE-OS 28 35 389).There are also low saturation magnetostrictions in 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 remainder 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).

Schließlich ist noch eine Gruppe von amorphen Legierungen mit niedriger Sättigungsmagnetostriktion ent- sprechend der Formel (FeaCobNic)x(SieBfPgCh)y bekannt, wobei a, b, c, e, f, g und h jeweils die Molbruchteile der entsprechenden Elemente und a + b + c = 1 sowie e - f + g + h = 1 sind und x bzw. y die Gesamtmenge der in der zugehörigen Klammer stehenden Elemente in Atom-% bedeuten und folgende Beziehungen gelten: 0,03 = a = 0,12; 0,40 ≤ b ≤ 0,85; 0 ≤ ey ≤ 25; 0 ≤ fy ≤ 30 und 0 ≤ g + h ≤ 0,8(e+f). Weiterhin können diese Legierungen, bezogen auf ihre Gesamtzusammensetzung, zusätzlich 0,5 bis 6 Atom-% wenigstens eines der Elemente Ti, Zr, V, Nb, Ta, Cr, Mo, W, Zn, Al, Ga, In, Ge, Sn, Pb, As, Sb und Bi enthalten (DE-OS 28 06 052).Finally, a group of amorphous alloys with low saturation magnetostriction according to the formula (Fe a Co b Ni c ) x (Si e B f P g C h ) y is known, where a, b, c, e, f, g and h are the mole fractions of the corresponding elements and a + b + c = 1 and e - f + g + h = 1 and x and y are the total amount in the corresponding Parenthesized elements in atomic% mean and the following relationships apply: 0.03 = a = 0.12; 0.40 ≤ b ≤ 0.85; 0 ≤ ey ≤ 25; 0 ≤ fy ≤ 30 and 0 ≤ g + h ≤ 0.8 (e + f). Furthermore, based on their total composition, 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).

Aufgabe der Erfindung ist es, eine weitere weichmagnetische Legierung zur Verfügung zu stellen, bei der der Betrag der Sättigungsmagnetostriktion |λs| ≤ 5·10-6 ist.The object of the invention is to provide a further soft magnetic alloy, in which the amount of saturation magnetostriction | λ s | ≤ 5 · 10 -6 .

Erfindungsgemäß werden so niedrige Sättigungsmagnetostriktionen bei einer Legierung der Zusammensetzung (CoaNibTcMndFee)100-t(SixByMz)t erreicht, wobei T wenigstens eines der Elemente Cr, Mo, W, V, Nb, Ta, Ti, Zr und Ef und M wenigstens eines der Elemente P, C, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi und Be sind und folgende Beziehungen gelten:

Figure imgb0001
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Figure imgb0012
 According to the invention, 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 Ef and M are at least one of the elements P, C, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi and Be and the following relationships apply:
Figure imgb0001
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Figure imgb0012

Hierbei bedeuten a, b, c, d, e bzw. x, y, z die jeweils auf die Gesamtsumme 1 normierten atomaren Anteile der zugehörigen Elemente an der Gesamtheit der in den entsprechenden Klammern stehenden Metalle bzw. Metalloide und (100-t) bzw. t den jeweiligen Anteil der Gesamtheit der in den zugehörigen Klammern stehenden Metalle bzw. Metalloide an der Legierung in Atom-%. Der Anteil eines einzelnen Elementes an der Legierung in Atom-% entspricht dem Produkt aus dem Index des entsprechenden Elementes und dem Index der zugehörigen Klammer. Beispielsweise ist der Siliziumanteil x' an der Legierung in Atom-% gleich x' = xt.Here, a, b, c, d, e and x, y, z mean the atomic proportions of the associated elements, standardized to the total sum 1, of the totality of the metals or metalloids and (100-t) or t the respective proportion of the total of the metals or metalloids in the associated brackets in the alloy in atomic%. The proportion of an individual element in the alloy in atomic% corresponds to the product of the index of the corresponding element and the index of the associated bracket. For example, the silicon portion x 'of the alloy in atomic% is equal to x' = xt.

Von den verschiedenen bekannten Legierungen mit kleiner Magretostriktion unterscheidet sich die erfindungsgemäße Legierung in ihrer Zusammensetzung insbesondere dadurch, daß Mangan mit einem Mindestgehalt d'min = dmin (100-tmax) = 0,65 Atom-% und Silizium mit einem Mindestgehalt x' = xt = 8 Atom-% als Zwangskomponente vorgeschrieben sind, sowie durch einenverhältnismäßig kleinen Höchstgehalt der Wahlkomponente Eisen von emax(100-tmin) = 1,64 Atom-%.The composition of the alloy according to the invention differs from the various known alloys with small magretostriction in particular in that manganese with a minimum content d ' min = d min (100-t max ) = 0.65 atom% and silicon with a minimum content x' = xt = 8 atom% are prescribed as a compulsory component, as well as a relatively small maximum content of the optional component iron of e max (100-t min ) = 1.64 atom%.

Überraschenderweise hat sich bei der erfindungsgemäßen Legierung gezeigt, daß durch eine entsprechende Bemessung des Mangangehaltes die Magnetostriktionskonstante bis auf Null verringert werden kann. Das Silizium hat eine Erhöhung der Kristallisationstemperatur und eine Absenkung der Schmelztemperatur zur Folge und führt daher zu einer verbesserten Herstellbarkeit der amorphen Legierung. Infolge der Verringerung der Differenz zwischen Schmelz- und Kristallisationstemperatur ist nämlich die Abkühlungsgeschwindigkeit bei der Herstellung der amorphen Legierung weniger kritisch. Auch die Übergangselemente T erhöhen die Kristallisationstemperatur, während mit wachsendem Metalloidgehalt außerdem die Curietemperatur der Legierung erniedrigt wird. Beides hat eine bessere Langzeitstabilität der magnetischen Eigenschaften der Legierung zur Folge. Nach oben ist der Metalloidgehalt dadurch begrenzt, daß die Curietemperatur nicht soweit absinken darf, daß die Legierung bei einer normalen Temperatur nicht mehr ferromagnetisch ist.Surprisingly, it has been shown in the alloy according to the invention that the magnetostriction constant can be reduced to zero by appropriate measurement of the manganese content. The silicon has an increase in the crystallization temperature and a decrease in the melting temperature and therefore leads to an improved manufacturability of the amorphous alloy. As a result of reducing the difference between the melting and Kristallisationstem erature p Namely, the cooling rate in the preparation of the amorphous alloy is less critical. 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.

Besonders günstig ist es, wenn für den Metalloidanteil der anmeldungsgemäßen Legierung folgende Bedingungen erfüllt sind:

Figure imgb0013
Figure imgb0014
Figure imgb0015
 It is particularly favorable if the following conditions are met for the metalloid portion of the alloy according to the application:
Figure imgb0013
Figure imgb0014
Figure imgb0015

Der Mangangehalt, bei dem der Nulldurchgang der Magnetostriktionskonstante erfolgt, wird mit wachsendem Metalloidgehalt der Legierung sowie mit wachsenden Anteilen an Nickel und den sonstigen Übergangselementen T kleiner. Für den Mangangehalt der Legierungen mit einer Sättigungsmagnetostriktionskonstante λs= 0 gilt dabei näherungsweise die Beziehung d = 0,09 - 0,001 (t - 25 + 10b + 10c)2 mit der Nebenbedingung 0,01 ≤ d.The manganese content at which the magnetostriction constant passes through zero becomes smaller as the alloy's metalloid content increases and with increasing proportions of nickel and the other transition elements T. For the manganese content of the alloys with a saturation magnetostriction constant λ s = 0, the relationship d = 0.09 - 0.001 (t - 25 + 10b + 10c) 2 with the additional condition 0.01 ≤ d applies approximately.

Legierungen mit dem Betrag der Magnetostriktionskonstante |λs| ≤ finden sich vorzugsweise bei Mangangehalten, für die folgende Beziehungen gelten:

Figure imgb0016
Alloys with the magnitude of the magnetostriction constant | λ s | ≤ are preferably found for manganese contents, for which the following relationships apply:
Figure imgb0016

Magnetostriktionskonstanten |λs| ≤ 1·10-6 erhält man bei Mangangehalten, für die folgende Beziehungen gelten:

Figure imgb0017
Magnetostriction constants | λ s | ≤ 1 · 10 -6 is obtained for manganese contents, for which the following relationships apply:
Figure imgb0017

Die erfindungsgemäßen Legierungen zeigen bereits nach der Herstellung durch rasche Abkühlung aus der Schmelze gute weichmagnetische Eigenschaften, d.h. niedrige Koerzitivkraft, hohe Permeabilität und niedrige Wechselstromverluste. Durch eine Glühbehandlung unterhalb der Kristallisauionstemperatur können die magnetischen Eigenschaften insbesondere von aus der Legierung hergestellten Magnetkernen häufig noch weiter verbessert werden. Eine solche Wärmebehandlung kann bei Temperaturen von etwa 250 bis 500 C, vorzugsweise 300 bis 460°C, vorgenommen werden und etwa 10 Minuten bis 24 Stunden, vorzugsweise 30 Minuten bis 4 Stunden, dauern. Sie wird vorteilhaft in inerter Atmosphäre, beispielsweise Vakuum, Wasserstoff, Helium oder Argon, und in einem parallel zur Bandrichtung verlaufenden äußeren Magnetfeld, also einem magnetischen Längsfeld, mit einer Feldstärke zwischen 1 und 200 A/cm, vorzugsweise 5 bis 50 A/cm,vorgenommen.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.

Durch die Abkühlungsgeschwindigkeit nach der Wärmebehandlung läßt sich die Form der Magnetisierungskurve einstellen. So erhält man durch schnelles Abschrecken mit Abschreckungsgeschwindigkeiten zwischen 400 K und 10 000 K pro Stunde hohe Permeabilitäten bereits für kleine Aussteuerungen und niedrige Verluste bei hohen Frequenzen von beispielsweise 20 kHz. Durch langsame Abkühlung mit einer Abkühlungsgeschwindigkeit von etwa 20 bis 400 K pro Stunde in Anwesenheit des magnetischen Längsfeldes erhält man dagegen besonders hohe Maximalpermeabilitäten und kleine Koerzitivfeldstärken.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, for example, 20 kHz. By contrast, slow cooling at a cooling rate of about 20 to 400 K per hour in the presence of the longitudinal magnetic field gives particularly high maximum permeabilities and small coercive field strengths.

Anhand einiger Figuren und Beispiele soll die Erfindung noch näher erläutert werden.

  • Figur 1 zeigt die Abhängigkeit der Magnetostriktionskonstante vom Mangangehalt für Legierungen der Zusammensetzung Co75-d'Mnd'Si15B10.
  • Figur 2 zeigt den Einfluß einer Wärmebehandlung auf die Permeabilität einer Legierung der Zusammensetzung Co48,5Ni20Mn7,5Si11B13.
The invention will be explained in more detail with the aid of a few figures and examples.
  • FIG. 1 shows the dependence of the magnetostriction constant on the manganese content for alloys with the composition Co 75-d ' Mn d' Si 15 B 10 .
  • FIG. 2 shows the influence of a heat treatment on the permeability of an alloy of the composition Co 48.5 Ni 20 Mn 7.5 Si 11 B 13 .

Zunächst soll am Beispiel der Legierungen der Zusammensetzung Co75-d'Mnd'Si,15B10 die Abhängigkeit der Magnetostriktionskonstante vom Mangangehalt veranschaulicht werden. Hierzu wurden/in der folgenden Tabelle I aufgeführten Legierungen in Form etwa 0,04 mm dicker und 2mm breiter Bänder in an sich bekannter Weise dadurch hergestellt, daß die Elemente in einem Quarzgefäß mittels Erhitzung durch Induktion aufgeschmolzen und die Schmelze anschließend durch eine in dem Quarzgefäß befindliche Öffnung auf eine schnell rotierende Kupfertrommel aufgespritzt wurde. Eine anschließende Messung der Sättigungsmagnetostriktionskonstante λs ergab folgende Werte:

Figure imgb0018
First, 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 . For this purpose / in the following Table I alloys in the form of approximately 0.04 mm thick and 2 mm wide strips 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 subsequently melted by one in the quartz vessel sprayed opening located on a rapidly rotating copper drum has been. A subsequent measurement of the saturation magnetostriction constant λ s gave the following values:
Figure imgb0018

Außer λs ist in der vorstehenden Tabelle auch noch die Sättigungsmagnetisierung Js in T und die Koerzitivfeldstärke Hc in

Figure imgb0019
angegeben. Die Werte beziehen sich auf die Legierung im Herstellungszustand ohne nachfolgende Wärmebehandlung.In addition to λ s , the table above also shows the saturation magnetization J s in T and the coercive field strength H c in
Figure imgb0019
 specified. The values refer to the alloy in the production state without subsequent heat treatment.

Graphisch ist der Zusammenhang zwischen der Sättigungsmagnetostriktionskonstanten und dem Mangangehalt der Legierungen in Figur 1 dargestellt. Dabei ist an der Ordinate die Magnetostriktionskonstante und an der Abszisse der Mangangehalt d' = d (100-t) in Atom-% aufgetragen. Wie man aus Figur 1 sieht, besteht zwischen beiden Größen ein linearer Zusammenhang. Der Nulldurchgang der Magnetostriktionskonstante erfolgt bei einer Legierung mit etwa 7 Atom-% Mangan.The relationship between the saturation magnetostriction constant and the manganese content of the alloys is shown graphically in FIG. 1. The magnetostriction constant is plotted on the ordinate and the manganese content d '= d (100-t) in atomic% is plotted on the abscissa. As can be seen from Figure 1, there is a linear relationship between the two quantities. The zero crossing of the magnetostriction constant occurs with an alloy with about 7 atomic% manganese.

Bei den anderen anmeldungsgemäßen Legierungen liegen ähnliche Verhältnisse vor, wobei der Mangangehalt, bei dem der Nulldurchgang der Magnetostriktionskonstante erfolgt, mit zunehmenden Anteilen von Metalloiden, Nickel und Übergangsmetallen T abnimmt.Similar ratios exist for the other alloys according to the application, the manganese content at which the magnetostriction constant passes through zero decreasing with increasing proportions of metalloids, nickel and transition metals T.

In den Tabellen II bis IV sind eine Reihe weiterer anmeldungsgemäßer Legierungen zusammengestellt, die gemäß dem vorhergehenden Beispiel hergestellt wurden. Die in Tabelle II aufgeführten Legierungen haben besonders niedrige Magnetostriktionskonstanten λs, eine verhältnismäßig hohe Sättigungsinduktion J und bereits im Zustand nach der Herstellung ohne Wärmebehandlung eine sehr niedrige Koerzitivfeldstärke Hc, gemessen am gestreckten Band.

Figure imgb0020
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 λ s , a relatively high saturation induction J, and even in the state after production without heat treatment, a very low coercive force H c , measured on the stretched strip.
Figure imgb0020

Bei den in Tabelle III aufgeführten Legierungen liegt der Betrag der Magnetostriktionskonstante bei etwa 1·10-6.

Figure imgb0021
betragsmäßigFor the alloys listed in Table III, the magnitude of the magnetostriction constant is approximately 1 · 10 -6 .
Figure imgb0021
 in terms of amount

Weitere Legierungen mit/etwas höheren Magnetostriktionskonstanten sind in Tabelle IV aufgeführt.

Figure imgb0022
Other alloys with / somewhat higher magnetostriction constants are listed in Table IV.
Figure imgb0022

Am folgenden Beispiel soll der Einfluß der Wärmebehandlung erläutert werden.The following example explains the influence of heat treatment.

Aus einem gemäß dem ersten Beispiel hergestellten Band einer Legierung der Zusammensetzung Co48,5Ni20Mn7,5Si11B13 wurde ein Ringkern gewickelt, dessen Permeabilität in einem magnetischen Wechselfeld von 50 Hz gemessen wurde. Kurve 1 von Figur 2 zeigt die Abhängigkeit der Permeabilität von der Maximalamplitude des Magnetfeldes. Dabei ist die Permeabilität an der Ordinate, die Amplitude H des Magnetfeldes in

Figure imgb0023
an der Abszisse angegeben. Anschießend wurde der gleiche Kern unter Wasserstoff in einem magnetischen Längsfeld von etwa 10 A/cm etwa eine Stunde lang einer Wärmebehandlung bei 380° C unterzogen und anschließend im Magnetfeld mit einer Abkühlungsgeschwindigkeit von etwa 100 K/h abgekühlt. Die anschließend in einem magnetischen Wechselfeld von 50 Hz gemessenen Permeabilitäten sind in Kurve 2 von Figur 2 dargestellt.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 on the ordinate, the amplitude H of the magnetic field in
Figure imgb0023
 indicated on the abscissa. The same core was then subjected to a heat treatment at 380 ° C. for about one hour under hydrogen in a magnetic longitudinal field of about 10 A / cm and then cooled in a magnetic field at a cooling rate of about 100 K / h. The permeabilities subsequently measured in an alternating magnetic field of 50 Hz are shown in curve 2 of FIG. 2.

Die anmeldungsgemäßen Legierungen eignen sich insbesondere als Material für magnetische Abschirmungen, Tonköpfe und Magnetkerne, insbesondere wenn letztere bei höheren Frequenzen, beispielsweise bei 20 kHz, betrieben werden sollen. Ferner eignen sich die anmeldungsgemäßen Legierungen wegen ihrer niedrigen Magnetostriktion und ihrer bereits im Herstellungszustand sehr guten weichmagnetischen Eigenschaften insbesondere auch für Anwendungen, bei denen das weichmagmetische Material verformt werden muß und anschließend eine Wärmebehandlung nicht mehr möglich ist.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 subsequently heat treatment is no longer possible.

Claims (4)

1. Amorphe weichmagnetische Legierung, die Kobalt, Mangan, Silizium und Bor enthält, gekennzeichnet durch die Zusammensetzung
Figure imgb0024
wobei T wenigstens eines der Elemente Cr, Mo, W, V, Nb, Ta, Ti, Zr und Hf und M wenigstens eines der Elemente P, C, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi und Be sind und folgende Beziehungen gelten:
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
 1. Amorphous soft magnetic alloy containing cobalt, manganese, silicon and boron, characterized by the composition
Figure imgb0024
 where T at least one of the elements Cr, Mo, W, V, Nb, Ta, Ti, Zr and Hf and M at least one of the elements P, C, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi and Be and the following relationships apply:
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
 2. Amorphe weichmagnetische Legierung nach Anspruch 1, gekennzeichnet durch folgende Beziehungen:
Figure imgb0037
Figure imgb0038
Figure imgb0039
 2. Amorphous soft magnetic alloy according to claim 1, characterized by the following relationships:
Figure imgb0037
Figure imgb0038
Figure imgb0039
 3. Amorphe weichmagnetische Legierung nach einem der Ansprüche 1 oder 2, gekennzeichnet durch folgende Beziehungen:
Figure imgb0040
 3. Amorphous soft magnetic alloy according to one of claims 1 or 2, characterized by the following relationships:
Figure imgb0040
 4. Amorphe weichmagnetische Legierung nach Anspruch 3, gekennzeichnet durch folgende Beziehungen:
Figure imgb0041
 4. Amorphous soft magnetic alloy according to claim 3, characterized by the following relationships:
Figure imgb0041
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061290A2 (en) * 1981-03-20 1982-09-29 Matsushita Electric Industrial Co., Ltd. Magnetic head and method of producing same
EP0066356A1 (en) * 1981-03-31 1982-12-08 Masumoto Tsuyoshi Process for the production of fine amorphous metallic wires
EP0072574A2 (en) * 1981-08-18 1983-02-23 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic core material
EP0080521A1 (en) * 1981-11-26 1983-06-08 Allied Corporation Low magnetostriction amorphous metal alloys
EP0088244A1 (en) * 1982-03-04 1983-09-14 Allied Corporation Cobalt rich manganese containing near-zero magnetostrictive metallic glasses having high saturation induction
EP0121046A2 (en) * 1983-03-31 1984-10-10 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic head and magnetic head with an amorphous alloy
EP0121649A1 (en) * 1983-02-04 1984-10-17 Allied Corporation Amorphous antipilferage marker
EP0160166A1 (en) * 1981-11-26 1985-11-06 Allied Corporation Low magnetostriction amorphous metal alloys
EP0161394A1 (en) * 1981-11-26 1985-11-21 Allied Corporation Low magnetostriction amorphous metal alloys
EP0291726A2 (en) * 1987-05-21 1988-11-23 Vacuumschmelze GmbH Amorphous alloy for strip-shaped sensor elements
EP0378823A2 (en) * 1989-01-14 1990-07-25 Vacuumschmelze GmbH Use of a magnet core in an interface transformer
WO1994009172A1 (en) * 1992-10-16 1994-04-28 Allied-Signal Inc. IMPROVED HARMONIC MARKERS MADE FROM Fe-Ni BASED SOFT MAGNETIC ALLOYS HAVING NANOCRYSTALLINE STRUCTURE
USRE35042E (en) * 1983-02-04 1995-09-26 Allied Corporation Amorphous antipilferage marker
US6580348B1 (en) 1999-02-22 2003-06-17 Vacuumschmelze Gmbh Flat magnetic core

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5754251A (en) 1980-09-15 1982-03-31 Tdk Corp Amorphous magnetic alloy material
JPS57193005A (en) * 1981-05-23 1982-11-27 Tdk Corp Amorphous magnetic alloy thin belt for choke coil and magnetic core for the same
JPS5884957A (en) * 1981-11-14 1983-05-21 Matsushita Electric Ind Co Ltd Amorphous magnetic alloy
JPS58185743A (en) * 1982-04-24 1983-10-29 Tdk Corp Thin plate of amorphous magnetic alloy for magnetic head
US4637843A (en) * 1982-05-06 1987-01-20 Tdk Corporation Core of a noise filter comprised of an amorphous alloy
JPS59150414A (en) * 1982-12-23 1984-08-28 Toshiba Corp Reactor for semiconductor circuit
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 (en) * 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 Current transformer with DC current tolerance
DE10134056B8 (en) * 2001-07-13 2014-05-28 Vacuumschmelze Gmbh & Co. Kg Process for the production of nanocrystalline magnetic cores and apparatus for carrying out the process
US6749695B2 (en) 2002-02-08 2004-06-15 Ronald J. Martis Fe-based amorphous metal alloy having a linear BH loop
US6930581B2 (en) * 2002-02-08 2005-08-16 Metglas, Inc. Current transformer having an amorphous fe-based core
US6613275B1 (en) * 2002-07-19 2003-09-02 Metalor Technologies Sa Non-precious dental alloy
JP4445195B2 (en) * 2002-11-29 2010-04-07 株式会社東芝 Amorphous alloy ribbon and magnetic core using it
DE102005034486A1 (en) * 2005-07-20 2007-02-01 Vacuumschmelze Gmbh & Co. Kg Process for the production of a soft magnetic core for generators and generator with such a core
EP1918407B1 (en) * 2006-10-30 2008-12-24 Vacuumschmelze GmbH & Co. KG Iron-cobalt based soft magnetic alloy and method for its manufacture
US7771545B2 (en) 2007-04-12 2010-08-10 General Electric Company Amorphous metal alloy having high tensile strength and electrical resistivity
US9057115B2 (en) * 2007-07-27 2015-06-16 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron-cobalt-based alloy and process for manufacturing it
US8012270B2 (en) 2007-07-27 2011-09-06 Vacuumschmelze Gmbh & Co. Kg Soft magnetic iron/cobalt/chromium-based alloy and process for manufacturing it
US9312343B2 (en) 2009-10-13 2016-04-12 Cree, Inc. Transistors with semiconductor interconnection layers and semiconductor channel layers of different semiconductor materials

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2364131A1 (en) * 1972-12-26 1974-06-27 Allied Chem AMORPH METAL ALLOY AND THEIR USE
DE2546676A1 (en) * 1974-10-21 1976-04-29 Western Electric Co ELECTROMAGNETIC COMPONENT
DE2553003A1 (en) * 1974-11-29 1976-08-12 Allied Chem MAGNETIC DEVICES
DE2605615A1 (en) * 1975-02-15 1976-09-02 Tdk Electronics Co Ltd MAGNETIC HEAD
DE2708151A1 (en) * 1976-03-01 1977-09-08 Allied Chem MAGNETIC ALLOYS
DE2806052A1 (en) * 1977-02-18 1978-10-19 Tdk Electronics Co Ltd THERMALLY STABLE AMORPHIC MAGNETIC ALLOY
DE2835389A1 (en) * 1977-08-15 1979-03-01 Allied Chem MAGNETIC ALLOY
DE2855858A1 (en) * 1977-12-28 1979-07-05 Tokyo Shibaura Electric Co AMORPH ALLOY WITH HIGH MAGNETIC PERMEABILITY

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1505841A (en) * 1974-01-12 1978-03-30 Watanabe H Iron-chromium amorphous alloys
JPS5940900B2 (en) * 1974-07-01 1984-10-03 トウホクダイガク キンゾクザイリヨウケンキユウシヨチヨウ Amorphous iron alloy for high strength, fatigue resistance, general corrosion resistance, pitting corrosion resistance, crevice corrosion resistance, stress corrosion cracking resistance, and hydrogen embrittlement resistance
US4144058A (en) * 1974-09-12 1979-03-13 Allied Chemical Corporation Amorphous metal alloys composed of iron, nickel, phosphorus, boron and, optionally carbon
JPS5929644B2 (en) * 1974-12-24 1984-07-21 東北大学金属材料研究所長 Method for modifying magnetic properties of high magnetic permeability amorphous alloy
DE2555003A1 (en) * 1975-12-06 1977-06-16 Fraunhofer Ges Forschung Automatic learning process for industrial robots - employs optical sensors coupled to television display for determination of optimised coordinates
JPS59582B2 (en) * 1976-03-23 1984-01-07 東北大学金属材料研究所長 Amorphous alloy for magnetic heads with low magnetostriction and high wear resistance and its manufacturing method
US4116682A (en) * 1976-12-27 1978-09-26 Polk Donald E Amorphous metal alloys and products thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2364131A1 (en) * 1972-12-26 1974-06-27 Allied Chem AMORPH METAL ALLOY AND THEIR USE
DE2546676A1 (en) * 1974-10-21 1976-04-29 Western Electric Co ELECTROMAGNETIC COMPONENT
DE2553003A1 (en) * 1974-11-29 1976-08-12 Allied Chem MAGNETIC DEVICES
DE2605615A1 (en) * 1975-02-15 1976-09-02 Tdk Electronics Co Ltd MAGNETIC HEAD
DE2708151A1 (en) * 1976-03-01 1977-09-08 Allied Chem MAGNETIC ALLOYS
DE2806052A1 (en) * 1977-02-18 1978-10-19 Tdk Electronics Co Ltd THERMALLY STABLE AMORPHIC MAGNETIC ALLOY
DE2835389A1 (en) * 1977-08-15 1979-03-01 Allied Chem MAGNETIC ALLOY
DE2855858A1 (en) * 1977-12-28 1979-07-05 Tokyo Shibaura Electric Co AMORPH ALLOY WITH HIGH MAGNETIC PERMEABILITY

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061290A3 (en) * 1981-03-20 1983-05-25 Matsushita Electric Industrial Co., Ltd. Magnetic head and method of producing same
EP0061290A2 (en) * 1981-03-20 1982-09-29 Matsushita Electric Industrial Co., Ltd. Magnetic head and method of producing same
EP0066356A1 (en) * 1981-03-31 1982-12-08 Masumoto Tsuyoshi Process for the production of fine amorphous metallic wires
EP0072574A2 (en) * 1981-08-18 1983-02-23 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic core material
EP0072574A3 (en) * 1981-08-18 1983-09-14 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic core material
EP0160166A1 (en) * 1981-11-26 1985-11-06 Allied Corporation Low magnetostriction amorphous metal alloys
EP0080521A1 (en) * 1981-11-26 1983-06-08 Allied Corporation Low magnetostriction amorphous metal alloys
EP0161394A1 (en) * 1981-11-26 1985-11-21 Allied Corporation Low magnetostriction amorphous metal alloys
EP0088244A1 (en) * 1982-03-04 1983-09-14 Allied Corporation Cobalt rich manganese containing near-zero magnetostrictive metallic glasses having high saturation induction
US4553136A (en) * 1983-02-04 1985-11-12 Allied Corporation Amorphous antipilferage marker
EP0121649A1 (en) * 1983-02-04 1984-10-17 Allied Corporation Amorphous antipilferage marker
USRE35042E (en) * 1983-02-04 1995-09-26 Allied Corporation Amorphous antipilferage marker
EP0121046A2 (en) * 1983-03-31 1984-10-10 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic head and magnetic head with an amorphous alloy
EP0121046A3 (en) * 1983-03-31 1986-11-26 Kabushiki Kaisha Toshiba Amorphous alloy for magnetic head and magnetic head with an amorphous alloy
EP0291726A2 (en) * 1987-05-21 1988-11-23 Vacuumschmelze GmbH Amorphous alloy for strip-shaped sensor elements
EP0291726A3 (en) * 1987-05-21 1989-07-05 Vacuumschmelze Gmbh Amorphous alloy for strip-shaped sensor elements
EP0378823A2 (en) * 1989-01-14 1990-07-25 Vacuumschmelze GmbH Use of a magnet core in an interface transformer
EP0378823A3 (en) * 1989-01-14 1991-04-03 Vacuumschmelze GmbH Use of a magnet core in an interface transformer
WO1994009172A1 (en) * 1992-10-16 1994-04-28 Allied-Signal Inc. IMPROVED HARMONIC MARKERS MADE FROM Fe-Ni BASED SOFT MAGNETIC ALLOYS HAVING NANOCRYSTALLINE STRUCTURE
US6580348B1 (en) 1999-02-22 2003-06-17 Vacuumschmelze Gmbh Flat magnetic core

Also Published As

Publication number Publication date
EP0021101B1 (en) 1983-01-26
ATE2343T1 (en) 1983-02-15
JPS6218620B2 (en) 1987-04-23
US5200002A (en) 1993-04-06
DE2924280A1 (en) 1981-01-08
JPS563646A (en) 1981-01-14
DE3061764D1 (en) 1983-03-03
CA1166042A (en) 1984-04-24

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