EP0021101B1 - Amorphous soft magnetic alloy - Google Patents

Amorphous soft magnetic alloy Download PDF

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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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alloys
alloy
amorphous
elements
atomic
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German (de)
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EP0021101A1 (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, 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.

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, 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.

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 is understood to mean an alloy which is at least 50%, preferably at least 80%, amorphous.

Für jede amorphe 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 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.

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 2364131. DE-OS 25 53 003, DE-OS 2605615, 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 2364131. DE-OS 25 53 003, DE-OS 2605615, JP -OS 51-73923).

Von besonderem Interesse unter den amorphen weichmagnetischen Legierungen sind solche mit kleiner, möglichst verschwindend kleiner, Magnetostriktion. Eine möglichst kleine Sättigungsmagnetostriktion As 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, 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. 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 Legierungen hat 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 (CoxFe1-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, AI und P enthalten, ohne daß die erwünschten magnetischen Eigenschaften wesentlich verschlechtert werden (DE-OS 2708151).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%. 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 P without the desired magnetic properties are significantly deteriorated (DE-OS 2708151).

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 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).

Schließlich ist noch eine Gruppe von amorphen Legierungen mit niedriger Sättigungsmagnetostriktion entsprechend 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 each the Molar fractions of the corresponding elements and a + b + c = 1 and e - f + g + h = 1 are and x and y mean the total amount of the elements in the associated brackets in atomic% 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. Is 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 Hf und M wenigstens eines der Elemente P, C, AI, Ga, In, Ge, Sn, Pb, As, Sb, Bi und Be sind und folgende Beziehungen gelten :

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 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 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:
Figure imgb0001
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Hierbei bedeuten a, b, c, d, e bzw. x, y, z die jeweils auf die Gesamtsumme 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 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. For example, the silicon portion x 'of the alloy in atomic% is equal to x' = xt.

Von den verschiedenen bekannten Legierungen mit kleiner Magnetostriktion 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 low magnetostriction 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 atomic% 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 atomic%.

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 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. As a result of the reduction in the difference between the melting and crystallization temperatures, 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.

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

Figure imgb0013
Figure imgb0014
Figure imgb0015
 It is particularly advantageous 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 with increasing metalloid content of the alloy 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| ≤ 3 · 10-6 finden sich vorzugsweise bei Mangangehalten, für die folgende Beziehungen gelten :

  • 0,05 - 0.001 (t - 25 + 10b + 10c)2 ≤ d + e ≤
  • ≤0,13-0,001 (t-25+10b+10c)2
  • 0,01 ≤d≤0,13
  • 0 ≤e≤0,02.
Alloys with the magnitude of the magnetostriction constant | λ s | ≤ 3 · 10 -6 are preferably found for manganese contents, for which the following relationships apply:
  • 0.05 - 0.001 (t - 25 + 10b + 10c) 2 ≤ d + e ≤
  • ≤0.13-0.001 (t-25 + 10b + 10c) 2
  • 0.01 ≤d≤0.13
  • 0 ≤e≤0.02.

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

  • 0,07 - 0,001 (t - 25 + 10b + 10c)2 ≤ d + e ≤ ≤ 0,11 - 0,001 (t - 25 + 10b + 10C)2 0,01≤d≤0,13 0 < e % 0,02.
Magnetostriction constants | λ s | ≤ 1 · 10 -6 are obtained with manganese contents, for which the following relationships apply:
  • 0.07 - 0.001 (t - 25 + 10b + 10c) 2 ≤ d + e ≤ ≤ 0.11 - 0.001 (t - 25 + 10b + 10 C ) 2 0.01≤d≤0.13 0 <e % 0.02.

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 Kristallisationstemperatur 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 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.

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 with 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.Si15B10 die Abhängigkeit der Magnetostriktionskonstante vom Mangangehalt veranschaulicht werden. Hierzu wurden die in der folgenden Tabelle 1 aufgeführten Legierungen in Form etwa 0,04 mm dicker und 2 mm 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 hs ergab folgende Werte :

Figure imgb0016
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, 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:
Figure imgb0016

Außer λs ist in der vorstehenden Tabelle auch noch die Sättigungsmagnetisierung J, in T und die Koerzitivfeldstärke He in mA/cm 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, 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.

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 Js und bereits im Zustand nach der Herstellung ohne Wärmebehandlung eine sehr niedrige Koerzitivfeldstärke He, gemessen am gestreckten Band.

Figure imgb0017
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 s and, even in the state after production without heat treatment, a very low coercive force H e , measured on the stretched strip.
Figure imgb0017

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

Figure imgb0018
For the alloys listed in Table III, the magnitude of the magnetostriction constant is approximately 1 · 10 -6 .
Figure imgb0018

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

Figure imgb0019
Other alloys with slightly higher magnetostriction constants are listed in Table IV.
Figure imgb0019

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 mA/cm an der Abszisse angegeben. Anschließend 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 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.

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 weichmagnetische 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 heat treatment is then no longer possible.

Claims (4)

1. An amorphous soft-magnetic alloy containing cobalt, manganese, silicon and boron, characterised by the composition
Figure imgb0036
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 :
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
2. An amorphous soft-magnetic alloy according to Claim 1, characterised by the following relationships:
Figure imgb0049
Figure imgb0050
Figure imgb0051
3. An amorphous soft-magnetic alloy according to Claim 1 or Claim 2, characterised by the following relationships :
0,05 - 0,001 (t - 25 + 10b + 10c)2 ≤ d + e≤ ≤ 0,13 - 0,001 (t - 25 - 10b + 10c)2 0,01 ≤d≤0,13 0 ≤e≤0,02.
4. An amorphous soft-magnetic alloy according to Claim 3, characterised by the following relationships :
0,07 - 0,001 (t - 25 + 10b + 10c)2 ≤ d + e ≤ ≤ 0,11 - 0,001 (t - 25 + 10b + 10c)2 0,01 ≤ d ≤ 0,13 0 ≤ e ≤ 0,02.
EP80102997A 1979-06-15 1980-05-29 Amorphous soft magnetic alloy Expired EP0021101B1 (en)

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