EP0482064B1 - Verres metalliques riches en fer presentant une induction de saturation elevee ainsi que des proprietes ferromagnetiques plus douces superieures a des vitesses de magnetisation elevees - Google Patents

Verres metalliques riches en fer presentant une induction de saturation elevee ainsi que des proprietes ferromagnetiques plus douces superieures a des vitesses de magnetisation elevees Download PDF

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EP0482064B1
EP0482064B1 EP90911005A EP90911005A EP0482064B1 EP 0482064 B1 EP0482064 B1 EP 0482064B1 EP 90911005 A EP90911005 A EP 90911005A EP 90911005 A EP90911005 A EP 90911005A EP 0482064 B1 EP0482064 B1 EP 0482064B1
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alloy
magnetic
ranges
induction
alloys
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EP0482064A1 (fr
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V. R. V. Ramanan
Carl H. Smith
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Honeywell International Inc
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AlliedSignal Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F3/00—Cores, Yokes, or armatures

Definitions

  • This invention relates to iron-rich metallic glass alloys having high saturation induction that evidence particularly superior soft ferromagnetic properties when subjected to high magnetization rates.
  • Glassy metal alloys are metastable materials lacking any long range order. They are conveniently prepared by rapid quenching from the melt using processing techniques that are conventional in the art. Examples of such metallic glasses and methods for their manufacture are disclosed in U.S. Patents No. 3,856,513, 4,067,732 and 4,142,571. The advantageous soft magnetic characteristics of metallic glasses, as disclosed in these patents, have been exploited in their wide use as materials in a variety of magnetic cores, such as in distribution transformers, switch-mode power supplies and tape recording heads.
  • pulse power applications Applications for soft magnetic cores, in a particular class that is now receiving increased attention, are generically referred to as pulse power applications.
  • a low average power input with a long acquisition time, is converted to an output that has high peak power delivered in a short transfer time.
  • very fast magnetization reversals ranging up to 100 T/ ⁇ s (or 100 MT/s)
  • pulse power applications include saturable reactors for magnetic pulse compression and for protection of circuit elements during turn on, and pulse transformers in linear induction particle accelerators.
  • Metallic glasses are very well suited for pulse power applications because of their high resistivities and thin ribbon geometry, which allow low losses under fast magnetization reversals.
  • Metallic Glasses in High-Energy Pulsed-Power Systems by C.H. Smith, in Glass...Current Issues , A.J. Wright and J. Dupuy, eds., (NATO ASI Series E, No. 92, Martinus Nijhoff Pub., Dordrecht, The Netherlands, 1985) pp.
  • metallic glasses due to their noncrystalline nature, bear no magneto-crystalline anisotropy and, consequently, may be annealed to deliver very large flux swings, with values approaching the theoretical maximum value of twice the saturation induction of the material, under rapid magnetization rates.
  • metallic glass materials have led to their use as core materials in various pulse power applications: in high power pulse sources for linear induction particle accelerators, as induction modules for coupling energy from the pulse source to the beam of these accelerators, as magnetic switches in power generators, in inertial confinement fusion research, and in magnetic modulators for driving excimer lasers.
  • the core material is initially "parked” in, or biased into, a specific magnetic state through the imposition of appropriate external magnetic fields.
  • a large, negative d.c. field will place the core material in a negatively saturated state.
  • the direction in which the core material will be driven into saturation during the application is referred to as the positive direction.
  • a subsequent removal of this field will position the core material at negative remanence.
  • the former procedure allows for a maximum flux swing of twice the saturation induction in the core material but, as a matter of convenience, the latter procedure, known as the pulse reset, is most commonly employed.
  • the maximum flux swing is then the sum of the remanent and saturation inductions.
  • the term “maximum flux swing”, as used herein, connotes a value that is determined by the sum of the remanent and saturation inductions.
  • Metallic glasses may easily be annealed to yield a value for B r , the remanent induction, that is very close to B s , the saturation induction.
  • the input that is to be compressed, or transformed, in the application, is then applied to the core material.
  • METGLAS® 2605CO nominal composition: Fe66Co18B15Si1
  • Allied-Signal Inc. is a high induction metallic glass alloy currently used in many of the pulse power applications recited above. This metallic glass is taught by U.S. Patent No. 4,321,090, wherein metallic glasses having a high saturation induction are disclosed.
  • the saturation induction of this glassy alloy is about 1.75 T.
  • the high cobalt content in this alloy imparts a high value for the magnetic anisotropy energy and, consequently, high core losses.
  • the value of about 900 J/m3 for the magnetic anisotropy energy in this alloy is among the highest obtained in metallic glasses.
  • a maximum flux swing of only about 3.2 T is attainable from this alloy.
  • the high Co content in this alloy leads to high raw material costs.
  • the cores used in pulse power applications may contain as much as 100 kg of core material per core, and considering that Co had been classified as a strategic material, a more economical alloy containing substantially reduced levels of Co is highly desirable.
  • a metallic glass alloy that contains no cobalt is METGLAS®2605SC (nominal composition: Fe81B 13.5 Si 3.5 C2), available from Allied-Signal Inc. This alloy is disclosed in U.S. Patent No. 4,219,355.
  • the low magnetic anisotropy energy (about 100 J/m3) of this alloy has been exploited in certain pulse power applications.
  • the lower saturation induction (about 1.57 T) and a correspondingly lower maximum flux swing (about 2.9 T) available from this alloy have deterred widespread use of this alloy in pulse power applications.
  • a metallic glass alloy that offered a combination of high induction (large flux swings) and low magnetic anisotropy energy would be highly desirable for the purpose of pulse power applications.
  • An additional advantage would be derived if such an alloy were to offer economy in production costs.
  • compositions of the invention are that found in normal commercial practice.
  • the metallic glasses of this invention are especially suitable for use in large magnetic cores used in various pulse power applications requiring high magnetization rates.
  • Representative of such applications are high-power pulse sources for linear induction particle accelerators, induction modules for coupling energy from the pulse source to the beam of these accelerators, magnetic switches in power generators in inertial confinement fusion research and magnetic modulators for driving excimer lasers.
  • Other uses include cores of airborne transformers, current transformers, ground fault interrupters and switch-mode power supplies.
  • the alloys of the invention are preferably at least 90% glassy, and most preferably 100% glassy, as established by X-ray diffraction. Furthermore, the glassy alloys of the invention that evidence a saturation induction of at least 1.6 T are especially preferred from the point of view of pulse power applications.
  • metallic glasses of the invention include Fe75Co6B14Si3C2, Fe77Co6B12Si3C2, Fe78Co6B12Si3C1, Fe79Co2B14Si3C2, Fe76Co6B15Si1C2, Fe77Co7B12Si2C2, Fe80Co6B11Si1C2 and Fe78Co6B12Si2C2.
  • Co in the alloys serves to increase the saturation induction level.
  • Cobalt contents of less than 2 at.% provide only marginal increases in saturation induction levels over alloys containing no cobalt.
  • the rate of increase of saturation induction due to the presence of Co reduces substantially above about 8 at.% Co, and higher levels of Co are therefore not desired because of the substantial cost of the element.
  • the alloys of the invention contain carbon for a variety of reasons: First, the introduction of C in the alloys has been found to increase even further the saturation induction levels of the alloys. This increase is especially notable in alloys containing between 11 and 14 at.% boron. For this reason, alloys of the invention having a B content ranging between 11 at.% and 14 at.% are more preferred.
  • the second reason for requiring the presence of C in the alloys of the invention is that the handling characteristics of an iron-rich alloy melt are improved with the introduction of C in the melt. From the point of view of large scale production of rapidly solidified ribbons of metallic glasses, improved handling characteristics of the alloy melt are an important asset.
  • the magnetic anisotropy energy of a ferromagnetic material is a measure of the energy required to rotate the magnetic moments in the material away from an established, preferred direction of alignment. The magnitude of this energy dictates the ease with which a particular domain structure may be established in the material.
  • FIG. 1 This figure is a schematic representation of the dynamic magnetization curves ("B-H loops") obtained from ferromagnetic materials which are subjected to high magnetization rates; H a is the applied magnetic field on the core material and ⁇ B is the flux swing obtained from the core material. As noted in the figure, this magnetization curve may be broken down to five regions (or parts) of magnetic response from the core material.
  • H a In region I, after a rapid increase usually limited by stray inductances, H a reaches a maximum and then actually decreases in many cases.
  • This peak in region II is associated with the establishment of bar shaped ferromagnetic domains spanning the ribbon thickness, the minimum in H corresponding to the attainment of an efficient domain wall spacing. Magnetization progresses by the motion of these bar domain walls in region III, costing very little in H a .
  • the higher mobility of the portion of the domain walls near the ribbon surface soon results in a single domain wall which encircles the interior of the ribbon, and is generally referred to as the "sandwich" domain. While no detailed understanding is available, it is generally understood in the art that the magnetization behavior in region IV is related to the progression of this sandwich domain, before saturation is attained in region V.
  • the area enclosed by the dynamic magnetization curve and the ordinate axis in Figure 1 represents the core loss of the magnetic core material.
  • This core loss is really a "half-cycle" loss, in that only one-half of a conventional hysteresis loop is being traversed by the material.
  • all references to core losses of materials, whether of this invention or not, in connection with the description of this invention will imply these half-cycles losses.
  • the magnetic anisotropy energy of metallic glasses in the Fe-B-Si system may be reduced by the addition of suitable amounts of a fourth element.
  • carbon is one such element.
  • other such elements include Mo, Nb, V, and Cr.
  • the effect of Si in the alloys of the invention is to reduce the saturation induction but increase the thermal stability of the glassy state of the alloys by increasing their crystallization temperatures.
  • the maximum level of 4 at.% Si in the alloys of this invention defines an acceptable balance between these two effects of Si.
  • Coated ribbons were obtained by dipping as-cast ribbons in a diluted solution of colloidal silica. The host solution was isopropanol in the commercially available colloid, and methanol was used for dilution.
  • Figure 3 compares the losses obtained from the same alloy of Figure 2 with the losses obtained from two prior art metallic glasses that are now commercially used in cores for pulse power applications, as a function of the magnetization rate. Fifty millimeter wide ribbons of all three alloys referred in this figure were coated as detailed above, and annealed under their respective optimal conditions. The reduced levels of losses attainable, over a wide range of magnetization rates, in the alloy of this invention are illustrated by this figure.
  • H (ave.) the average field
  • dB/dt the measured core loss
  • Figure 4 in a plot of H (ave.) vs. (dB/dt) for the same ribbons as in Figure 3, uses this performance measure to illustrate the superior performance characteristics typical of the alloys of this invention, when compared with commercial, prior art metallic glasses.
  • Glassy metal alloys designated as samples no. 1 to 47 in Table III, were rapidly quenched from the melt following the techniques taught by Narasimhan in U.S. Patent No. 4,142,571, the disclosure of which is hereby incorporated by reference thereto. All casts were made in a vacuum chamber, using 0.025 to 0.100 kg melts comprising constituent elements of high purity. The resulting ribbons, typically 25 to 30 ⁇ m thick and about 6 mm wide, were determined to be free of crystallinity by x-ray diffractometry using Cu-K ⁇ radiation and differential scanning calorimetry. Some of the alloys were also cast separately as 50 mm wide ribbons, to facilitate a direct comparison with commercial alloys. Each of the alloys was at least 80% glassy, most of them more than 90% glassy and, in many instances, the alloys were 100% glassy. Ribbons of these glassy metal alloys were strong, shiny, hard and ductile.
  • a commercial vibrating sample magnetometer was used for the measurement of the saturation magnetic moment of these alloys. As-cast ribbon from a given alloy was cut into several small squares (approximately 2 mm X 2 mm), which were randomly oriented about a direction normal to their plane, their plane being parallel to a maximum applied field of about 755 kA/m. By using the measured mass density, the saturation induction, B s , was then calculated. The density of many of these alloys was measured using standard techniques invoking Archimedes' Principle.
  • the core losses were measured on closed-magnetic path toroidal samples.
  • the toroidal samples were prepared by winding continuous ribbons of the glassy metal alloys onto ceramic bobbins (about 40 mm O.D.), so that the mean magnetic path length was about 0.13 m.
  • Each toroidal sample contained between about 0.002 kg and 0.01 kg of ribbon. All toroids were annealed prior to the loss measurements. The anneal temperatures ranged between about 573 K and 623 K, the anneal times ranged between about 900 s and 3600 s, and an external field ranging in strength from about 400 A/m to about 1600 A/m was imposed on the toroids throughout the anneal cycle.
  • the toroids were driven by discharging a low inductance capacitor bank through a set of insulated primary windings, numbering from about 3 to about 10.
  • the current in the primary windings was measured using a commercial current probe.
  • a one turn secondary winding provided a voltage proportional to (dB/dt), the magnetization rate.
  • the voltage and current waveforms were digitized at 20 ns per point and recorded on a digital oscilloscope.
  • the core loss, the applied field and the maximum flux swing were then calculated by processing these stored waveforms.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Hard Magnetic Materials (AREA)
  • Glass Compositions (AREA)

Abstract

Un alliage de verre métallique magnétique présente une induction de saturation élevée ainsi qu'une faible énergie d'anisotropie magnétique combinées. La composition dudit alliage est décrite par la formule FeaCobBcSidCe, dans laquelle 'a' - 'e' sont exprimés en pourcentage d'atome, 'a' est compris entre environ 72 et environ 84, 'b' est compris entre environ 2 et environ 8, 'c' est compris entre environ 11 et environ 16, 'd' est compris entre environ 1 et environ 4, et 'e' est compris entre 0 et environ 4, et jusqu'à environ 1 atome pourcent de Mn étant facultativement présent. Ledit alliage est adapté notamment pour être utilisé dans de grands noyaux magnétiques associés à des applications de puissance à impulsion nécessitant des vitesses de magnétisation élevées. On peut citer à titre d'exemple desdites applications des sources à impulsions de puissance élevées pour des accélérateurs de particules à induction linéaire, des modules d'induction destinés à coupler de l'énergie provenant d'une source d'impulsions au faisceau de ces accélérateurs, des commutateurs magnétiques dans des générateurs de puissance en recherche de fusion à confinement inertiel, des modulateurs magnétiques destinés à exciter des lasers à excimère, et analogues.

Claims (5)

  1. Alliage de verre métallique magnétique qui est au moins vitreux à environ 80 %, ayant une composition définie par la formule FeaCobBcSidCe, dans laquelle "a" - "e" sont des atomes en %, "a" est compris entre 72 et 84, "b" entre 2 et 8, "c" entre 11 et 16, "d" entre 1 et 4, et "e" entre 0,5 et 2, avec jusqu'à 1 atome % de Mn étant présent en option dans l'alliage, ledit alliage ayant été recuit, et ayant une induction de saturation comprise entre 1,55 T et 1,75 T, une énergie de l'anisotropie magnétique comprise entre 300 J/m³ et 400 J/m³ et une oscillation à courant continu entre rémanence negative et saturation positive comprise entre 2,9T et 3,2T.
  2. Alliage selon la revendication 1, dans lequel "d" est compris entre 1 et 2.
  3. Alliage selon la revendication 1 ou 2, dans lequel "c" est compris entre 11 et 14.
  4. Alliage selon la revendication ayant la composition :
    Fe₇₅Co₆B₁₄Si₃C₂, Fe₇₇Co₆B₁₂Si₃C₂, Fe₇₈Co₆B₁₂Si₃C₁, Fe₇₉Co₂B₁₄Si₃C₂, Fe₇₆Co₆B₁₅Si₁C₂, Fe₇₇Co₇B₁₂Si₂C₂, Fe₈₀Co₆B₁₁Si₁C₂, Fe₇₈Co₆B₁₂Si₂C₂ ou Fe₇₉Co₆B₁₂Si₂C₁.
  5. Noyau magnétique destiné à être utilisé à des vitesses d'aimantation supérieures à 1 MT/s, ledit noyau ayant comme matériau un alliage tel que revendiqué dans l'une quelconque des revendications précédentes.
EP90911005A 1989-07-14 1990-06-20 Verres metalliques riches en fer presentant une induction de saturation elevee ainsi que des proprietes ferromagnetiques plus douces superieures a des vitesses de magnetisation elevees Expired - Lifetime EP0482064B1 (fr)

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US37976389A 1989-07-14 1989-07-14
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EP (1) EP0482064B1 (fr)
JP (1) JPH0689438B2 (fr)
CA (1) CA2059267C (fr)
DE (1) DE69004962T2 (fr)
WO (1) WO1991001563A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE69004580T2 (de) * 1990-01-24 1994-03-10 Allied Signal Inc Eisenreiche metallische gläser mit hoher sättigungsinduktion und guten weichmagnetischen eigenschaften mit hohen magnetisierungsgeschwindigkeiten.
JPH07335450A (ja) * 1994-06-10 1995-12-22 Hitachi Metals Ltd 小型トランスおよびそれを用いたインバータ回路ならびに放電管点灯回路
US6930581B2 (en) * 2002-02-08 2005-08-16 Metglas, Inc. Current transformer having an amorphous fe-based core
US20160329139A1 (en) * 2015-05-04 2016-11-10 Carpenter Technology Corporation Ultra-low cobalt iron-cobalt magnetic alloys

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219355A (en) * 1979-05-25 1980-08-26 Allied Chemical Corporation Iron-metalloid amorphous alloys for electromagnetic devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4226619A (en) * 1979-05-04 1980-10-07 Electric Power Research Institute, Inc. Amorphous alloy with high magnetic induction at room temperature
US4321090A (en) * 1980-03-06 1982-03-23 Allied Corporation Magnetic amorphous metal alloys

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4219355A (en) * 1979-05-25 1980-08-26 Allied Chemical Corporation Iron-metalloid amorphous alloys for electromagnetic devices

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JPH04502649A (ja) 1992-05-14
CA2059267C (fr) 2000-06-06
EP0482064A1 (fr) 1992-04-29
DE69004962T2 (de) 1994-03-24
DE69004962D1 (de) 1994-01-13
WO1991001563A1 (fr) 1991-02-07
JPH0689438B2 (ja) 1994-11-09
CA2059267A1 (fr) 1991-01-15

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