EP0072893A1 - Metallic glasses having a combination of high permeability, low coercivity, low AC core loss, low exciting power and high thermal stability - Google Patents

Metallic glasses having a combination of high permeability, low coercivity, low AC core loss, low exciting power and high thermal stability Download PDF

Info

Publication number
EP0072893A1
EP0072893A1 EP82104504A EP82104504A EP0072893A1 EP 0072893 A1 EP0072893 A1 EP 0072893A1 EP 82104504 A EP82104504 A EP 82104504A EP 82104504 A EP82104504 A EP 82104504A EP 0072893 A1 EP0072893 A1 EP 0072893A1
Authority
EP
European Patent Office
Prior art keywords
atom percent
low
boron
iron
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82104504A
Other languages
German (de)
French (fr)
Other versions
EP0072893B1 (en
Inventor
Ryusuke Hasegawa
Gordon Edward Fish
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Allied Corp
Original Assignee
Allied Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allied Corp filed Critical Allied Corp
Publication of EP0072893A1 publication Critical patent/EP0072893A1/en
Application granted granted Critical
Publication of EP0072893B1 publication Critical patent/EP0072893B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02—Alloys based on vanadium, niobium, or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent

Definitions

  • the invention relates to metallic glasses having high permeability, low magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability.
  • metallic glasses are metastable materials lacking any long range order.
  • X-ray diffraction scans of glassy metal alloys show only a diffuse halo similar to that observed for inorganic oxide glasses.
  • Metallic glasses have been disclosed in U.S. Patent 3,856,513, issued December 24, 1974 to H.S. Chen et al. These alloys include compositions having the formula M a Y b Z c , where M is a metal selected from the group consisting of iron, nickel, cobalt, vanadium and chromium, Y is an element selected from the group consisting of phosphorus, boron and carbon and Z is an element selected from the group consisting of aluminum, silicon, tin, germanium, indium, antimony and beryllium, "a” ranges from about 60 to 90 atom percent, "b” ranges from about 10 to 30 atom percent and "c” ranges from about 0.1 to 15 atom percent.
  • M is a metal selected from the group consisting of iron, nickel, cobalt, vanadium and chromium
  • Y is an element selected from the group consisting of phosphorus, boron and carbon
  • Z is an element selected from the group consisting of aluminum, silicon, tin,
  • metallic glassy wires having the formula T i X j' where T is at least one transition metal and X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, beryllium and antimony, "i” ranges from about 70 to 87 atom percent and "j” ranges from about 13 to 30 atom percent.
  • T is at least one transition metal
  • X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, beryllium and antimony
  • i ranges from about 70 to 87 atom percent
  • j ranges from about 13 to 30 atom percent.
  • Metallic glasses are also disclosed in U.S. Patent No. 4,067,732 issued January 10, 1978. These glassy alloys include compositions having the formula M a M' b Cr c M" d B e , where M is one iron group element (iron, cobalt and nickel), M' is at least one of the two remaining iron group elements, M" is at least one element of vanadium, manganese, molybdenum, tungsten, niobium and tantalum, B is boron, "a” ranges from about 40 to 85 atom percent, “b” ranges from 0 to about 45 atom percent, "c” and “d” both range from 0 to about 20 atom percent and “e” ranges from about 15 to 25 atom percent, with the provision that "b", "c” and “d” cannot be zero simultaneously.
  • Such glassy alloys are disclosed as having an unexpected combination of improved ultimate tensile strength, improved hardness and improved thermal stability.
  • metallic glasses possessing a combination of higher permeability, lower magnetostriction, lower coercivity, lower core loss, lower exciting power and higher thermal stability than prior art metallic glasses are required for specific applications such as tape recorder head, relay cores, transformers and the like.
  • metallic glasses having a combination of high permeability, low magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability.
  • the metallic glasses consist essentially of about 66 to 82 atom percent of iron, from 1 to about 8 atom percent of which metal may be replaced with at least one of nickel and cobalt, about 1 to about 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, about 17 to 28 atom percent of boron, from 0.5 to about 6 atom percent of boron being, optionally, replaced with silicon and up to about 2 atom percent of boron being, optionally, replaced with carbon, plus incidental impurities.
  • the metallic glasses of the invention are suitable for use in tape recorder heads, relay cores, transformers and the like.
  • the metallic glasses of the invention are characterized by a combination of high permeability, low saturation magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability.
  • the glassy alloys of the invention consist essentially of about 66 to 82 atom percent iron, from 1 to about 8 atom percent of which metal may be replaced with at least one of nickel and cobalt, about 1 to 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, about 17 to 28 atom percent of boron, from 0.5 to about 6 atom percent of which metalloid may be replaced with silicon and up to 2 atom percent of which metalloid may be replaced with carbon, plus incidental impurities.
  • a concentration of less than about 1 atom percent of Cr, Mo, W, V, Nb, Ta, Ti, Zr and/or Hf does not result in sufficient improvement of the properties of permeability, saturation magnetostriction, coercivity, ac core loss and thermal stability.
  • a concentration o greater than about 6 atom percent of at least one of these elements results in an unacceptably low Curie temperature.
  • the metal content is preferably substantially iron, with up to about 8 atom percent nickel and/or cobalt in order to compensate the reduction of the room temperature saturation magentiza- tion due to the presence of chromium, molybdenum, tungsten, niobium, tantalium, titanium, zirconium and/or hafnium.
  • nickel increases permeability.
  • Examples of metallic glasses of the invention include Fe 80 Ni 1 Mo 1 B 16 Si 2 , Fe 76 Ni 4 Mo 2 B 17.5 Si 0.5 Fe 75 Ni 2 Co 2 Mo 3 B 16 Si 2 , F 75 Co 4 Mo 3 B 16 Si 2 , Fe75Ni4Mo3B16Si2, Fe 77 Ni 2 Mo 3 B 16 Si 2 , Fe 75 Ni 4 Mo 3 B 14 Si 4 , Fe 71 Ni 4 Mo 3 B 17 Si 5 , Fe 74 Ni 4 Mo 4 B 16 Si 2 , Fe 70 Ni 6 Mo 6 B 15 Si 3 , Fe 75 Ni 4 V 3 B 14 Si 2 C 2 , Fe 71 Ni 4 Mo 3 B 16 Si 4 C 2 , Fe78Ni2Mo2B12Si4C2, Fe 78 Ni 2 Cr 2 B 16 Si 2 , Fe 75 Ni 4 Nb 3 B 16 Si 2 , Fe 75 Ni 4 W 3 B 16 Si 2 , Fe75Ni4V3B16Si2' Fe 79 Ni 4 Ta 1 B 16 Si 2 , Fe 75 Ni 4 Ti 3 B 16 Si 2
  • chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafrium raises the crystallization temperature while simultaneously lowering the Curie temperature of the glassy alloy.
  • the increased separation of these temperatures provides ease of magnetic annealing, that is, thermal annealing at a temperature near the Curie temperature.
  • thermal annealing at a temperature near the Curie temperature.
  • annealing a magnetic material close to its Curie temperature generally results in improved properties.
  • annealing can be easily accomplished at elevated temperatures near the Curie temperature and below the crystallization temperature. Such annealing cannot be carried out for many alloys similar to those of the invention but lacking these elements.
  • too high a concentration of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafnium reduces the Curie temperature to a level that may be undesirable in certain applications.
  • chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafnium concentration is about 2 to 4 atom percent.
  • the metalloid content consist essentially of (1) substantially boron with a small amount of silicon, (2) boron plus silicon and (3) boron and silicon plus a small amount of carbon.
  • the metalloid content ranges from about 17 to 28 atom percent for maximum thermal stability.
  • Preferred metallic glass systems are as follows:
  • Magnetic permeability is the ratio of induction to applied magnetic field. A higher permeability renders a material more useful in certain applications such as tape recorder heads, due to the increased response.
  • the frequency dependence of permeability of the glassy alloys of the invention is similar to that of the 4-79 Permalloys in the medium-to-high frequency range (1-50 kHz), and at higher frequencies (about 50 kHz to 1 MHz), the permeability is comparable to that of the supermalloys.
  • a heat-treated Fe 7s Ni 4 Mo 3 B 16 si 2 metallic glass has permeability of 24,000 while the best-heat-treated prior art Fe40Ni36M04B20 metallic glass has a permeability of 14,000 at 1 kHz and the induction level of 0.01 Tesla.
  • Saturation magnetostriction is the change in length under the influence of a saturating magnetic field.
  • a lower saturation magnetostriction renders a material more useful in certain application such as tape recorder heads.
  • Magnetostriction is usually discussed in terms of the ratio of the change in length to the original length, and is given in ppm.
  • Prior art iron with metallic glasses evidence saturation magnetostric- tions of about 30 ppm as do metallic glasses without the presence of the any of the elements belonging to the IVB, VB and VIB columns of the periodic table such as molybdenum.
  • a prior art iron rich metallic glass designated for use in high frequency applications and having the composition Fe 79 B 16 Si 5 has a saturation magnetostriction of about 30 ppm.
  • a metallic glass of the invention having the composition Fe 75 Ni 4 Mo 3 B 16 Si 2 has a saturation magnetostriction of about 20 ppm.
  • a lower saturation magnetostriction leads to a lower phase angle between the exciting field and the resulting induction. This results in lower exciting power as discussed below.
  • Ac core loss i's that energy loss dissipated as heat. It is the hysteresis in an ac field and is measured by the area of a B-H loop for low frequencies (less than about 1 kHz) and from the complex imput power in the exciting coil for high frequencies (about 1 kHz to 1 MHz).
  • the major portion of the ac core loss at high frequencies arises from the eddy current generated during flux change.
  • a smaller hystersis loss and hence a smaller coercivity is desirable.
  • a lower core loss renders a material more useful in certain applications such as tape recorder heads and transformers. Core loss is discussed in units of watts/kg.
  • Prior art heat-treated metallic glasses typically evidence ac core losses of about 0.05 to 0.1 watts/kg at an induction of 0.1 Tesla and at the frequency range of 1 kHz.
  • a prior art heat-treated metallic glass having the composition Fe40Ni36Mo4B20 has an a c core loss of 0.07 watts/kg at an induction of 0.1 Tesla and at the frequency of 1 kHz
  • a metallic glass having the composition Fe 76 Mo 4 B 20 has an ac core loss of 0.08 watts/kg at an induction of 0.1 Tesla and at the same frequency.
  • a metallic glass alloy of the invention having the composition Fe 75 Ni 4 Mo 3 B 16 Si 2 has an ac core loss of 0.02 watts/kg at an induction of 0.1 Tesla and at the same frequency.
  • Exciting power is a measure of power required to maintain a certain flux density in a magnetic material. It is therefore desirable that a magnetic material to be used in magnetic devices has an exciting power as low as possible.
  • the phase shift is also related to the magnetostriction in such a way that a lower magnetostriction value leads to a lower phase shift. It is then advantageous to have the magnetostriction value as low as possible.
  • prior art iron-rich metallic glasses such as Fe 79 B 16 Si 5 have the magnetostriction value near 30 pp m , in contract to the magnetostriction value of about 20 ppm of the metallic glasses of the present invention.
  • This difference results in a considerable phase shift difference.
  • optimally annealed prior art metallic glass Fe 79 B 16 Si 5 has ⁇ near 70° while the metallic glasses of the present invention have 6 near 50°. This results, for a given core loss, in a higher exciting power by a factor of two for the prior art metallic glass than the metallic glass of the present invention.
  • Crystallization temperature is the temperature at which a metallic glass begins to crystallize. A higher crystallization temperature renders a material more useful in high temperature applications and, in conjunction with a Curie temperature that is substantially lower than the crystallization temperature, permits magnetic annealing just above the Curie temperature. Some metallic glasses crystallize in multiple steps. In such cases, the first crystallization temperature (the lowest value of the crystallization temperatures) is the meaningful one as far as the materials' thermal stability is concerned. The crystallization temperature as discussed herein is measured by differential scanning calorimetry. Prior art glassy alloys evidence crystallization temperatures of about 660 K to 750 K.
  • a metallic glass having the compo- s ition Fe 78 Mo 2 B 20 has a crystallization temperature of 680 K, while a metallic glass having the composition Fe 74 Mo 6 B 20 has a crystallization temperature of 750 K .
  • metallic glasses of the invention evidence increases in crystallization temperatures to a level above 750 K.
  • the magnetic properties of the metallic glasses of the present invention are improved by thermal treatment, characterized by choice of annealing temperatures (T a ), holding time (ta), applied magnetic field (either parallel or perpendicular to the ribbon direction and in the ribbon plane), and post-treatment cooling rate.
  • T a annealing temperatures
  • ta holding time
  • applied magnetic field either parallel or perpendicular to the ribbon direction and in the ribbon plane
  • post-treatment cooling rate post-treatment cooling rate.
  • the optimal properties are obtained after an anneal which causes the controlled precipitation of a certain number of crystalline particles from the glassy matrix. Under these conditions, for compositions having boron content ranging from about 17 to 20 atom percent, the discrete particles have a body-centered cubic structure.
  • the particles are composed essentially of iron, up to 22 atom percent of the iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium, hafnium, silicon and carbon.
  • the discrete particles consist essentially of a mixture of particles, a major portion of which mixture contains particles having a crystalline Fe 3 B structure.
  • the particles of such portion are composed of iron and boron, up to 14 atom percent of the iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium and up to 2 atom percent of the boron being adapted to be replaced by carbon.
  • a small number of such particles introduces a certain decrease in the average domain wall spacing with concomitant decrease in core loss. Too large a number of particles increases the coercivity and thus the hysteresis loss.
  • a metallic glass of the present invention with composition Fe75Ni4Mo3B16Si2 has a combination of low loss and high permeability with a coercivity of only 2 A/m when optimally annealed.
  • an optimally annealed prior art metallic glass Fe79Bl6Sis has a coercivity of about 8 A/m.
  • the crystalline particle size in the optimally heat-treated materials of the present invention ranges between 100 and 300nm, and their volume fraction is less than 1%.
  • the interparticle spacing is of the order of 1-10 ⁇ m.
  • the metallic glasses of the invention have a combination of high permeability, low saturation magnetostriction, low coercivity, low ac core loss, low exciting power and high crystallization temperature and are useful as tape heads, relay cores, transformers and the like.
  • the metallic glasses of the invention are prepared by cooling a melt of the desired composition at a rate of at least about 10 "C/sec, employing quenching techniques well known to the metallic glass art; see e.g., U.S. Patent 3,856,513.
  • the metallic glasses are substantially completely glassy, that is, at least 90% glassy, and consequently possess lower coercivities and are more ductile than less glassy alloys.
  • a variety of techniques are available for fabricating continuous ribbon, wire, sheet, etc. Typically, a particular composition is selected, powders or granules of the requisite elements in the desired portions are melted and homogenized and the molten alloy is rapidly quenched on a chill surface such as a rapidly rotating cylinder.
  • Ribbons having compositions given by Fe 100-a-b-c-d Ni a Mo b B c Si d and having dimensions about 1 to 2.5 cm wide and about 25 to 50 ⁇ m thick were formed by squirting a melt of the particular composition by overpressure of argon onto a rapidly rotating copper chill wheel (surface speed about 3000 to 6000 ft/min).
  • Molybdenum content was varied from 1 to 6 atom percent, for which substantially glassy ribbons were obtained. Molybdenum content higher than 6 atom percent reduced the Curie temperature to an unacceptable low value.
  • Permeability, magnetostriction, core loss, magnetization and coercive force were measured by conventional techniques employing B-H loops, metallic strain gauges and a vibrating sample magnetometer. Curie temperature and crystallization temperature were measured respectively by an induction method and differential scanning calorimetry. The measured values at room temperature saturation induction, Curie temperature, room temperature saturation magnetostriction and the first crystallization temperature are summarized in Table I below. The magnetic properties of these glassy alloys after annealing are presented in Table II. Optimum annealing conditions for the metallic glass Fe 75 Ni 4 Mo 3 B 16 Si 2 and the obtained results are summarized in Table III. Frequency dependence of permability and ac core loss of this optimally annealed alloy are listed in Table IV.
  • the presence of molybdenum is seen to increase the permeability and the crystallization temperature and to lower the ac core loss, exciting power and magnetostriction.
  • the optimally heat-treated metallic glass Fe 7S Ni 4 M0 3 B 16 Si 2 of the present invention has a coercivity reaching as low as 2.5 A/m and yet has a low core loss of 6.5 w/kg and permeability of 12500 at 50 kHz and at the induction level of 0.1 Tesla.
  • the combination of these properties make these compositions suitable for high frequency transformer and tape-head applications.
  • Ribbons having compositions given by Fe 100-a-b-c-d M-M'-B-Si when M is nickel and/or cobalt, M' is one of the elements chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, and having dimensions about 1 cm wide and about 25 to 50Pm thick were formed as in Example 1.
  • Metal “M'” content was varied from 1 to 6 atom percent, for which substantially glassy ribbons were obtained. Higher metal “M'” content reduced the Curie temperature to an unacceptably low value.
  • a combination of low ac core loss and high permeability at high frequency is achieved in the metallic glasses of the present invention.
  • the thermal stability is also shown to be excellent as evidenced by high crystallization temperature.
  • the metal "M'” content was varied from 1 to 6 atom percent, and the carbon content "e” was up to 2 atom percent for which substantially glassy ribbons were obtained.
  • the metal "M'” content greater than about 6 atom percent reduced the Curie temperature to an unacceptably low value.
  • the magnetic and thermal data are summarized in Table VII below.
  • the magnetic properties of these metallic glasses after annealing are presented in Table VIII.
  • a combination of low ac core loss, high permeability, and high thermal stability of the metallic glasses of the present invention renders these compositions suitable in the magnetic cores of transformers, recording heads and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Powder Metallurgy (AREA)
  • Adornments (AREA)

Abstract

Metallic glasses having high permeability, low magnetostriction, low coercivity low ac core loss, low exciting power and high thermal stability are disclosed. The metallic glasses consist essentially of about 66 to 82 atom percent iron, from 1 to about 8 atom percent of said iron being, optionally replaced with nickel and/or cobalt, about 1 to 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, about 17 to 28 atom percent of boron, 0.5 to 6 atom percent of said boron being, optionally, replaced with silicon and up to 2 atom percent of boron being, optionally, replaced with carbon, plus incidental impurities. Such metallic glasses are especially suited for use in tape heads, relay cores, transformers and the like.

Description

    Field of the Invention
  • The invention relates to metallic glasses having high permeability, low magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability.
    • Description of the Prior Art
  • As is known, metallic glasses are metastable materials lacking any long range order. X-ray diffraction scans of glassy metal alloys show only a diffuse halo similar to that observed for inorganic oxide glasses.
  • Metallic glasses (amorphous metal alloys) have been disclosed in U.S. Patent 3,856,513, issued December 24, 1974 to H.S. Chen et al. These alloys include compositions having the formula MaYbZc, where M is a metal selected from the group consisting of iron, nickel, cobalt, vanadium and chromium, Y is an element selected from the group consisting of phosphorus, boron and carbon and Z is an element selected from the group consisting of aluminum, silicon, tin, germanium, indium, antimony and beryllium, "a" ranges from about 60 to 90 atom percent, "b" ranges from about 10 to 30 atom percent and "c" ranges from about 0.1 to 15 atom percent. Also disclosed are metallic glassy wires having the formula TiXj' where T is at least one transition metal and X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, beryllium and antimony, "i" ranges from about 70 to 87 atom percent and "j" ranges from about 13 to 30 atom percent. Such materials are conveniently prepared by rapid quenching from the melt using processing techniques that are now well-known in the art.
  • Metallic glasses are also disclosed in U.S. Patent No. 4,067,732 issued January 10, 1978. These glassy alloys include compositions having the formula MaM'bCrcM"dBe, where M is one iron group element (iron, cobalt and nickel), M' is at least one of the two remaining iron group elements, M" is at least one element of vanadium, manganese, molybdenum, tungsten, niobium and tantalum, B is boron, "a" ranges from about 40 to 85 atom percent, "b" ranges from 0 to about 45 atom percent, "c" and "d" both range from 0 to about 20 atom percent and "e" ranges from about 15 to 25 atom percent, with the provision that "b", "c" and "d" cannot be zero simultaneously. Such glassy alloys are disclosed as having an unexpected combination of improved ultimate tensile strength, improved hardness and improved thermal stability.
  • These disclosures also mention unusual or unique magnetic properties for many metallic glasses which fall within the scope of the broad claims. However, metallic glasses possessing a combination of higher permeability, lower magnetostriction, lower coercivity, lower core loss, lower exciting power and higher thermal stability than prior art metallic glasses are required for specific applications such as tape recorder head, relay cores, transformers and the like.
    • SUMMARY OF THE INVENTION
  • In accordance with the invention, metallic glasses having a combination of high permeability, low magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability are provided. The metallic glasses consist essentially of about 66 to 82 atom percent of iron, from 1 to about 8 atom percent of which metal may be replaced with at least one of nickel and cobalt, about 1 to about 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, about 17 to 28 atom percent of boron, from 0.5 to about 6 atom percent of boron being, optionally, replaced with silicon and up to about 2 atom percent of boron being, optionally, replaced with carbon, plus incidental impurities. The metallic glasses of the invention are suitable for use in tape recorder heads, relay cores, transformers and the like.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The metallic glasses of the invention are characterized by a combination of high permeability, low saturation magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability. The glassy alloys of the invention consist essentially of about 66 to 82 atom percent iron, from 1 to about 8 atom percent of which metal may be replaced with at least one of nickel and cobalt, about 1 to 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, about 17 to 28 atom percent of boron, from 0.5 to about 6 atom percent of which metalloid may be replaced with silicon and up to 2 atom percent of which metalloid may be replaced with carbon, plus incidental impurities. A concentration of less than about 1 atom percent of Cr, Mo, W, V, Nb, Ta, Ti, Zr and/or Hf does not result in sufficient improvement of the properties of permeability, saturation magnetostriction, coercivity, ac core loss and thermal stability. A concentration o greater than about 6 atom percent of at least one of these elements results in an unacceptably low Curie temperature.
  • Iron provides high saturation magnetization at room temperature. Accordingly the metal content is preferably substantially iron, with up to about 8 atom percent nickel and/or cobalt in order to compensate the reduction of the room temperature saturation magentiza- tion due to the presence of chromium, molybdenum, tungsten, niobium, tantalium, titanium, zirconium and/or hafnium. The addition of nickel increases permeability.
  • Examples of metallic glasses of the invention include Fe80Ni1Mo1B16Si2, Fe76Ni4Mo2B17.5Si0.5 Fe75 Ni2Co2Mo3B16Si2, F75Co4Mo3B16Si2, Fe75Ni4Mo3B16Si2, Fe77Ni2Mo3B16Si2, Fe75Ni4Mo3B14Si4, Fe71Ni4Mo3B17Si5, Fe74Ni4Mo4B16Si2, Fe70Ni6Mo6B15Si3, Fe75Ni4V3B14Si2C2, Fe71Ni4Mo3B16Si4C2, Fe78Ni2Mo2B12Si4C2, Fe78Ni2Cr2B16Si2, Fe75Ni4Nb3B16Si2, Fe75Ni4W3B16Si2, Fe75Ni4V3B16Si2' Fe79Ni4Ta1B16Si2, Fe75Ni4Ti3B16Si2, Fe75Ni4Zr3B16Si2, Fe79Ni4Hf1B16Si2, Fe72Ni2Mo2B22Si2, Fe70Ni2Mo2B22Si4, and Fe70Ni2Mo2B24Si2 (the subscripts are in atom percent). The purity of all alloys is that found in normal commercial practice.
  • The presence of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafrium raises the crystallization temperature while simultaneously lowering the Curie temperature of the glassy alloy. The increased separation of these temperatures provides ease of magnetic annealing, that is, thermal annealing at a temperature near the Curie temperature. As is well-known, annealing a magnetic material close to its Curie temperature generally results in improved properties. As a consequence of the increase in crystallization temperature with increase in the concentration of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium, and/or hafnium, annealing can be easily accomplished at elevated temperatures near the Curie temperature and below the crystallization temperature. Such annealing cannot be carried out for many alloys similar to those of the invention but lacking these elements. On the other hand, too high a concentration of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafnium reduces the Curie temperature to a level that may be undesirable in certain applications. For metallic glasses in which boron and silicon are the major and minor metalloid constituents respectively, a preferred range of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and/or hafnium concentration is about 2 to 4 atom percent.
  • It is preferred that the metalloid content consist essentially of (1) substantially boron with a small amount of silicon, (2) boron plus silicon and (3) boron and silicon plus a small amount of carbon. Preferably, the metalloid content ranges from about 17 to 28 atom percent for maximum thermal stability.
  • Preferred metallic glass systems are as follows:
    • 1. Fe-M-Mo-B-Si: Fe100-a-b-c-dMaMobBcSid, where M is at least one of nickel and cobalt. When (c+d) is about 18, the preferred ranges of a,b,c and d are from about 2 to 8, from about 1 to 4, from about 14 to 17.5 and from about 0.5 to 4, respectively. When (c+d) is about 22, the preferred ranges for a,b,c and d are from about 2 to 8, from about 1 to 6, from about 15 to 20.5 and from about 0.5 to 6, respectively. When (c+d) is close to 25, the preferred ranges of a, b, c and d are from about 2 to 8, from about 1 to 6, from about 21 to 25 and from about 1 to 6 respectively. These metallic glasses have a combination of saturation induction (Bs) of 1.0-1.4 Tesla, saturation magnetostriction (À s) between 12 and 24 ppm, Curie temperature (e f) between about 475 and 705 K and first crystallization temperature of 750-880 K. When optimally heat-treated, these alloys have excellent ac magnetic properties especially at high frequencies (f>103 Hz). The ac core loss (L) and exciting power (P ) taken at f = 50 kHzfand the induction level of Bm = 0.1 Tesla of, for example, a heat-treated Fe75Ni4Mo3B16Si2 metallic glass are 6.5 W/kg and 13.4 VA/kg, respectively. These values are to be compared with L = 7W/kg and Pe = 20 VA/kg for a a heat-treated prior art metallic glass of the same thickness having the composition Fe79B16Si5. The permeability P at Bm = 0.01 Tesla is 10 500 and 8000 for the heat-treated Fe75Ni3Mo4B16Si2 and Fe79B16Si5, respectively. The smaller saturation magnetostriction (λs) of about 20 ppm of the present alloy as compared to s λs = 30 ppm for the aforesaid prior art alloy makes the alloys of the present invention especially suited for magnetic device applications such as cores for high frequency transformers. Beyond f = 50 kHz, the alloys of the present invention have permeabilities comparable or higher than those for crystalline supermalloys which have Bs near 0.8 Tesla. The higher values of B for the present alloys make these alloys better suited than supermalloys for magnetic applications of f>50 kHz. Fe-M-M'-B-Si: Fe100-a-b-c-dMaM'bBcSid where M is nickel and/or cobalt and M' is selected from Cr, W, V, Nb, Ta, Ti, Zr or Hf. When (c+d) is about 18, the preferred ranges of a,b,c and d are about 2 to 8, from about 1 to 4, from about 14 to 17.5 and from about 0.5 to 4, respectively. When (c+d) is about 22, the preferred ranges for a,b,c and d are from about 2 to 8, from about 1 to 6, from about 16 to 21.5 and from about 0.5 to 6, respectively. When (c+d) is close to 25, the preferred ranges for a, b, c and d are from about 2 to 8, from about 1 to 6, from about 21 to 25 and from about 1 to 6 respectively. Fe-M-M'-B-Si-C: Fe100-a-b-c-d-eM aM'bBcSidCe wherein M is nickel and/or cobalt, and M' is selected from the group consisting of Cr, Mo, W, V, Nb, Ta, Ti, Zr or Hf. When (c+d) is about 18, the preferred ranges for a,b,c,d and e are from about 2 to 8, from about 1 to 4, from about 12 to 17.5, from about 0.5 to 4 and from 0 to 2, respectively. When (c+d) is about 22, the preferred ranges for a,b,c,d and e are from about 2 to 8, from about 1 to 6, from about 14 to 21.5, from about 0.5 to 6 and from about 0 to 2, respectively. When (c+d) is close to 25, the preferred ranges for a, b, c, d and e are from about 2 to 8, from about 1 to 6, from'about 20 to 27, from about 1 to 6 and from about 0 to 2 respectively.
  • Magnetic permeability is the ratio of induction to applied magnetic field. A higher permeability renders a material more useful in certain applications such as tape recorder heads, due to the increased response. The frequency dependence of permeability of the glassy alloys of the invention is similar to that of the 4-79 Permalloys in the medium-to-high frequency range (1-50 kHz), and at higher frequencies (about 50 kHz to 1 MHz), the permeability is comparable to that of the supermalloys. Especially noted is the fact that a heat-treated Fe7sNi4Mo3B16si2 metallic glass has permeability of 24,000 while the best-heat-treated prior art Fe40Ni36M04B20 metallic glass has a permeability of 14,000 at 1 kHz and the induction level of 0.01 Tesla.
  • Saturation magnetostriction is the change in length under the influence of a saturating magnetic field. A lower saturation magnetostriction renders a material more useful in certain application such as tape recorder heads. Magnetostriction is usually discussed in terms of the ratio of the change in length to the original length, and is given in ppm. Prior art iron with metallic glasses evidence saturation magnetostric- tions of about 30 ppm as do metallic glasses without the presence of the any of the elements belonging to the IVB, VB and VIB columns of the periodic table such as molybdenum. For example, a prior art iron rich metallic glass designated for use in high frequency applications and having the composition Fe79B16Si5 has a saturation magnetostriction of about 30 ppm. In contract, a metallic glass of the invention having the composition Fe75Ni4Mo3B16Si2 has a saturation magnetostriction of about 20 ppm. A lower saturation magnetostriction leads to a lower phase angle between the exciting field and the resulting induction. This results in lower exciting power as discussed below.
  • Ac core loss i's that energy loss dissipated as heat. It is the hysteresis in an ac field and is measured by the area of a B-H loop for low frequencies (less than about 1 kHz) and from the complex imput power in the exciting coil for high frequencies (about 1 kHz to 1 MHz). The major portion of the ac core loss at high frequencies arises from the eddy current generated during flux change. However, a smaller hystersis loss and hence a smaller coercivity is desirable. A lower core loss renders a material more useful in certain applications such as tape recorder heads and transformers. Core loss is discussed in units of watts/kg. Prior art heat-treated metallic glasses typically evidence ac core losses of about 0.05 to 0.1 watts/kg at an induction of 0.1 Tesla and at the frequency range of 1 kHz. For example, a prior art heat-treated metallic glass having the composition Fe40Ni36Mo4B20, has an ac core loss of 0.07 watts/kg at an induction of 0.1 Tesla and at the frequency of 1 kHz, while a metallic glass having the composition Fe76Mo4B20 has an ac core loss of 0.08 watts/kg at an induction of 0.1 Tesla and at the same frequency. In contrast, a metallic glass alloy of the invention having the composition Fe75Ni4Mo3B16Si2 has an ac core loss of 0.02 watts/kg at an induction of 0.1 Tesla and at the same frequency.
  • Exciting power is a measure of power required to maintain a certain flux density in a magnetic material. It is therefore desirable that a magnetic material to be used in magnetic devices has an exciting power as low as possible. Exciting power (P ) is related to the above-mentioned core loss (L) through the relationship L = Pe cos δ where δ is the phase shift between the exciting field and the resultant induction. The phase shift is also related to the magnetostriction in such a way that a lower magnetostriction value leads to a lower phase shift. It is then advantageous to have the magnetostriction value as low as possible. As mentioned earlier, prior art iron-rich metallic glasses such as Fe 79 B 16Si5 have the magnetostriction value near 30 ppm, in contract to the magnetostriction value of about 20 ppm of the metallic glasses of the present invention. This difference results in a considerable phase shift difference. For example, optimally annealed prior art metallic glass Fe79B16Si5 has δ near 70° while the metallic glasses of the present invention have 6 near 50°. This results, for a given core loss, in a higher exciting power by a factor of two for the prior art metallic glass than the metallic glass of the present invention.
  • Crystallization temperature is the temperature at which a metallic glass begins to crystallize. A higher crystallization temperature renders a material more useful in high temperature applications and, in conjunction with a Curie temperature that is substantially lower than the crystallization temperature, permits magnetic annealing just above the Curie temperature. Some metallic glasses crystallize in multiple steps. In such cases, the first crystallization temperature (the lowest value of the crystallization temperatures) is the meaningful one as far as the materials' thermal stability is concerned. The crystallization temperature as discussed herein is measured by differential scanning calorimetry. Prior art glassy alloys evidence crystallization temperatures of about 660 K to 750 K. For example, a metallic glass having the compo- sition Fe78Mo2B20 has a crystallization temperature of 680 K, while a metallic glass having the composition Fe 74 Mo 6 B 20 has a crystallization temperature of 750 K. In contrast, metallic glasses of the invention evidence increases in crystallization temperatures to a level above 750 K.
  • The magnetic properties of the metallic glasses of the present invention are improved by thermal treatment, characterized by choice of annealing temperatures (Ta), holding time (ta), applied magnetic field (either parallel or perpendicular to the ribbon direction and in the ribbon plane), and post-treatment cooling rate. For the present alloys, the optimal properties are obtained after an anneal which causes the controlled precipitation of a certain number of crystalline particles from the glassy matrix. Under these conditions, for compositions having boron content ranging from about 17 to 20 atom percent, the discrete particles have a body-centered cubic structure. The particles are composed essentially of iron, up to 22 atom percent of the iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium, hafnium, silicon and carbon. For compositions having boron content ranging from about 21 to 25 atom percent and iron content ranging from about 69 to 78 atom percent, the discrete particles consist essentially of a mixture of particles, a major portion of which mixture contains particles having a crystalline Fe3B structure. The particles of such portion are composed of iron and boron, up to 14 atom percent of the iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium and up to 2 atom percent of the boron being adapted to be replaced by carbon. A small number of such particles introduces a certain decrease in the average domain wall spacing with concomitant decrease in core loss. Too large a number of particles increases the coercivity and thus the hysteresis loss. A metallic glass of the present invention with composition Fe75Ni4Mo3B16Si2 has a combination of low loss and high permeability with a coercivity of only 2 A/m when optimally annealed. In contrast to this, an optimally annealed prior art metallic glass Fe79Bl6Sis has a coercivity of about 8 A/m. The crystalline particle size in the optimally heat-treated materials of the present invention ranges between 100 and 300nm, and their volume fraction is less than 1%. The interparticle spacing is of the order of 1-10µm.
  • In summary, the metallic glasses of the invention have a combination of high permeability, low saturation magnetostriction, low coercivity, low ac core loss, low exciting power and high crystallization temperature and are useful as tape heads, relay cores, transformers and the like.
  • The metallic glasses of the invention are prepared by cooling a melt of the desired composition at a rate of at least about 10 "C/sec, employing quenching techniques well known to the metallic glass art; see e.g., U.S. Patent 3,856,513. The metallic glasses are substantially completely glassy, that is, at least 90% glassy, and consequently possess lower coercivities and are more ductile than less glassy alloys.
  • A variety of techniques are available for fabricating continuous ribbon, wire, sheet, etc. Typically, a particular composition is selected, powders or granules of the requisite elements in the desired portions are melted and homogenized and the molten alloy is rapidly quenched on a chill surface such as a rapidly rotating cylinder.
    • EXAMPLES Example 1: Fe-Ni-Mo-B-Si
  • Ribbons having compositions given by Fe100-a-b-c-dNiaMobBcSid and having dimensions about 1 to 2.5 cm wide and about 25 to 50 µm thick were formed by squirting a melt of the particular composition by overpressure of argon onto a rapidly rotating copper chill wheel (surface speed about 3000 to 6000 ft/min).
  • Molybdenum content was varied from 1 to 6 atom percent, for which substantially glassy ribbons were obtained. Molybdenum content higher than 6 atom percent reduced the Curie temperature to an unacceptable low value.
  • Permeability, magnetostriction, core loss, magnetization and coercive force were measured by conventional techniques employing B-H loops, metallic strain gauges and a vibrating sample magnetometer. Curie temperature and crystallization temperature were measured respectively by an induction method and differential scanning calorimetry. The measured values at room temperature saturation induction, Curie temperature, room temperature saturation magnetostriction and the first crystallization temperature are summarized in Table I below. The magnetic properties of these glassy alloys after annealing are presented in Table II. Optimum annealing conditions for the metallic glass Fe75Ni4Mo3B16Si2 and the obtained results are summarized in Table III. Frequency dependence of permability and ac core loss of this optimally annealed alloy are listed in Table IV.
  • The presence of molybdenum is seen to increase the permeability and the crystallization temperature and to lower the ac core loss, exciting power and magnetostriction. Especially noted is the fact that the optimally heat-treated metallic glass Fe7SNi4M03 B 16 Si 2 of the present invention has a coercivity reaching as low as 2.5 A/m and yet has a low core loss of 6.5 w/kg and permeability of 12500 at 50 kHz and at the induction level of 0.1 Tesla. The combination of these properties make these compositions suitable for high frequency transformer and tape-head applications.
    Figure imgb0001
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
    • Example 2: Fe-Ni-M-B-Si System
  • Ribbons having compositions given by Fe100-a-b-c-dM-M'-B-Si when M is nickel and/or cobalt, M' is one of the elements chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, and having dimensions about 1 cm wide and about 25 to 50Pm thick were formed as in Example 1.
  • Metal "M'" content was varied from 1 to 6 atom percent, for which substantially glassy ribbons were obtained. Higher metal "M'" content reduced the Curie temperature to an unacceptably low value.
  • The magnetic and thermal data are summarized in Table V below. The magnetic properties of these glassy alloys after annealing are presented in Table VI.
  • Low field magnetic properties of these metallic glasses were comparable to those for the metallic glasses containing molybdenum (Example 1).
  • A combination of low ac core loss and high permeability at high frequency is achieved in the metallic glasses of the present invention. The thermal stability is also shown to be excellent as evidenced by high crystallization temperature. These improved combination of properties of the metallic glasses of the present invention renders these compositions suitable in the magnetic cores of transformers, tape-recording heads and the like.
  • Table V. Examples of the room temperature saturation induction, Bs, Curie temperature, θf, saturation magnetostriction, Xs, and the first crystallization temperature, Tc, for the metallic glasses having the composition Fe100-a-b-c-dMaM'bBcSid where M is at least one of nickel and cobalt, and M' = Cr, Mo, W, V, Nb, Ta, Ti, Zr or Hf.
    Figure imgb0008
  • Table VI. Core loss (L), exciting power (Pe) and permeability (µ) taken at f = 50 kHz, and Bm= 0.1 Tesla on the heat-treated metallic glasses having the composition Fe100-a-b-c-dMaM'bBcSid where M = Ni, and/or Co, and M' = Cr, Mo1, W, V, Nb, Ta, Ti, Zr or Hf. The annealing temperatures are indicated by Ta and the holding time is 15 min. for allthe materials.
    Figure imgb0009
  • Table VII. Saturation induction (Bs), Curie temperature (θf), stauration magnetostriction (λs) and the first crystallization temperature (Tcl) of the metallic glasses having the composition Fe100-a-b-c-d-eNiaMbBcSidCe Where M' = Cr, Mo, W, V, Nb, Ta, Ti, or Zr.
    Figure imgb0010
    • Example 3: Fe-Ni-M-B-Si-C System
  • Ribbons having compositions given by Fe100-a-b-c-d-eNiaM'bBcSidCe where M = Cr, Mo, W, V, Nb, Ta, Ti, or Zr and having dimensions about 1 cm wide and about 25 to 50 µm thick were formed as in Example 1. The metal "M'" content was varied from 1 to 6 atom percent, and the carbon content "e" was up to 2 atom percent for which substantially glassy ribbons were obtained. The metal "M'" content greater than about 6 atom percent reduced the Curie temperature to an unacceptably low value.
  • The magnetic and thermal data are summarized in Table VII below. The magnetic properties of these metallic glasses after annealing are presented in Table VIII. A combination of low ac core loss, high permeability, and high thermal stability of the metallic glasses of the present invention renders these compositions suitable in the magnetic cores of transformers, recording heads and the like.
  • Table VIII. Core loss (L), exciting power (Pe) and permeability (µ) taken at f = 50 kHz and B = 0.1 Tesla on the heat-treated metallic glasses having the composition Fe100-a-b-c-d-eNiaM'bBcSidCe where M' = Cr, Mo, W, V, Nb or Ta. Annealing temperatures are indicated by Ta and the holding time is 15 min. for all the materials.
    Figure imgb0011
  • Having thus described the invention in rather full detail, it will be understood that this detail need not be strictly adhered to but that various changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the present invention as defined by the subjoined claims.

Claims (10)

1. A metallic glass that is substantially completely glassy having a combination of high permability, low magnetostriction, low coercivity, low ac core loss, low exciting power and high thermal stability consisting essentially of 66 to 82 atom percent of iron, from 1 to 8 atom percent of said iron being, optionally, replaced with at least one element selected from the group consisting of nickel, cobalt and mixtures thereof, 1 to 6 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium, 17 to 28 atom percent of boron, from 0.5 to 6 atom percent of said boron being, optionally, replaced with silicon and up to 2 atom percent of boron being, optionally, replaced with carbon, plus incidental impurities.
2. The metallic glass of claim 1, in which the metal consists essentially of 62 to 79 atom percent iron, 2 to 8 atom percent of at least one element selected from the group consisting of nickel, cobalt and mixtures thereof, and 2 to 4 atom percent of at least one element selected from the group consisting of chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and hafnium.
3. The metallic glass of claim 1, in which the replacement of boron with silicon and carbon provides said glass with a metalloid element selected from the group consisting of substantially boron and from .5 to 4 atom percent silicon, and boron plus silicon together with from 0 to 2 atom percent carbon.
4. The metallic glass of claim 3, in which said metalloid element ranges from 17 to 26 atom percent.
5. The metallic glass of claim 1, consisting essentially of 70 to 79 atom percent iron, about 2 to 4 atom percent of at least one element selected from the group consisting of nickel, cobalt and mixtures thereof, 2 to 4 atom percent of an element selected from the group consisting of molybdenum and chromium and 17 to 22 percent of an element selected from the group consisting of boron, silicon and mixtures thereof.
6. An alloy of claim 1 which is at least 85 percent amorphous, said alloy being characterized by the presence therein of discrete particles of its constituents, said particles having an average size ranging from about 0.1 µm to 0.3 µm and an average interparticle spacing of about 1 pm to 10 µm.
7. An alloy of claim 6, in which said discrete particles occupy and an average volume fraction of 0.005 to 0.01.
8. The method of enhancing the magnetic properties of the alloy recited in claim 1, comprising the step of annealing said alloy at a temperature and for a time sufficient to induce precipitation of discrete particles in said amorphous metal matrix.
9. A method as recited in claim 8, wherein the discrete particles consist essentially of a mixture of particles a portion of which mixture contains particles having a body-centered cubic structure, said particles being composed essentially of iron, up to 22 atom percent of said iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium, havnium, silicon, and carbon.
10. A method as recited in claim 8, wherein the discrete particles consist essentially of a mixture of particles a portion of which mixture contains particles having a crystalline Fe3B structure, said particles of said portion being composed of iron and boron, up to 14 atom percent of said iron being adapted to be replaced by at least one of nickel, cobalt, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium, and hafnium, and up to 2 atom percent of said boron being adapted to be replaced by carbon.
EP82104504A 1981-08-21 1982-05-24 Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability Expired EP0072893B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US29516581A 1981-08-21 1981-08-21
US295165 1981-08-21
US31951481A 1981-11-09 1981-11-09
US319514 1981-11-09

Publications (2)

Publication Number Publication Date
EP0072893A1 true EP0072893A1 (en) 1983-03-02
EP0072893B1 EP0072893B1 (en) 1986-12-03

Family

ID=26968961

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82104504A Expired EP0072893B1 (en) 1981-08-21 1982-05-24 Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability

Country Status (6)

Country Link
EP (1) EP0072893B1 (en)
JP (1) JPH0639663B2 (en)
KR (1) KR870001283B1 (en)
AU (1) AU557318B2 (en)
CA (1) CA1222646A (en)
DE (1) DE3274562D1 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0175222A1 (en) * 1984-09-17 1986-03-26 Energy Conversion Devices, Inc. Method of preparing a hard magnet by addition of a quench rate range broadening additive and a hard magnet prepared thereby
US4588452A (en) * 1983-03-16 1986-05-13 Allied Corporation Amorphous alloys for electromagnetic devices
US5160379A (en) * 1986-12-15 1992-11-03 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
US5474624A (en) * 1992-09-14 1995-12-12 Alps Electric Co., Ltd. Method of manufacturing Fe-base soft magnetic alloy
WO1996032518A1 (en) * 1995-04-13 1996-10-17 Alliedsignal Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
US5619174A (en) * 1993-07-30 1997-04-08 Alps Electric Co., Ltd. Noise filter comprising a soft magnetic alloy ribbon core
US6093261A (en) * 1995-04-13 2000-07-25 Alliedsignals Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
US6187112B1 (en) 1995-04-13 2001-02-13 Ryusuke Hasegawa Metallic glass alloys for mechanically resonant marker surveillance systems
EP1848837A2 (en) * 2005-02-11 2007-10-31 The Nanosteel Company Improved glass stability, glass forming ability, and microstructural refinement
US7935198B2 (en) 2005-02-11 2011-05-03 The Nanosteel Company, Inc. Glass stability, glass forming ability, and microstructural refinement
WO2012010940A2 (en) 2010-07-21 2012-01-26 Institut Polytechnique De Grenoble Amorphous metal alloy
WO2012010941A1 (en) 2010-07-21 2012-01-26 Rolex S.A. Watch-making or clock-making component comprising an amorphous metal alloy
US8704134B2 (en) 2005-02-11 2014-04-22 The Nanosteel Company, Inc. High hardness/high wear resistant iron based weld overlay materials

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4636365B2 (en) * 2004-07-05 2011-02-23 日立金属株式会社 Fe-based amorphous alloy ribbon and magnetic core
KR100904664B1 (en) * 2008-06-03 2009-06-25 주식회사 에이엠오 Magnetic core for electric current sensors
KR101698306B1 (en) * 2008-06-16 2017-01-19 더 나노스틸 컴퍼니, 인코포레이티드 Ductile metallic material and method for forming ductile metallic material
US11198927B1 (en) * 2019-09-26 2021-12-14 United States Of America As Represented By The Secretary Of The Air Force Niobium alloys for high temperature, structural applications

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052201A (en) * 1975-06-26 1977-10-04 Allied Chemical Corporation Amorphous alloys with improved resistance to embrittlement upon heat treatment
FR2376217A1 (en) * 1976-12-29 1978-07-28 Allied Chem GLASS METAL ALLOYS WITH IMPROVED MECHANICAL STRENGTH
FR2376218A1 (en) * 1976-12-29 1978-07-28 Allied Chem IMPROVED GLASS METAL GLASSES
DE2806052A1 (en) * 1977-02-18 1978-10-19 Tdk Electronics Co Ltd THERMALLY STABLE AMORPHIC MAGNETIC ALLOY
US4140525A (en) * 1978-01-03 1979-02-20 Allied Chemical Corporation Ultra-high strength glassy alloys
DE2855858A1 (en) * 1977-12-28 1979-07-05 Tokyo Shibaura Electric Co AMORPH ALLOY WITH HIGH MAGNETIC PERMEABILITY

Family Cites Families (2)

* 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
US4409041A (en) * 1980-09-26 1983-10-11 Allied Corporation Amorphous alloys for electromagnetic devices

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052201A (en) * 1975-06-26 1977-10-04 Allied Chemical Corporation Amorphous alloys with improved resistance to embrittlement upon heat treatment
FR2376217A1 (en) * 1976-12-29 1978-07-28 Allied Chem GLASS METAL ALLOYS WITH IMPROVED MECHANICAL STRENGTH
FR2376218A1 (en) * 1976-12-29 1978-07-28 Allied Chem IMPROVED GLASS METAL GLASSES
DE2806052A1 (en) * 1977-02-18 1978-10-19 Tdk Electronics Co Ltd THERMALLY STABLE AMORPHIC MAGNETIC ALLOY
DE2855858A1 (en) * 1977-12-28 1979-07-05 Tokyo Shibaura Electric Co AMORPH ALLOY WITH HIGH MAGNETIC PERMEABILITY
US4140525A (en) * 1978-01-03 1979-02-20 Allied Chemical Corporation Ultra-high strength glassy alloys

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4588452A (en) * 1983-03-16 1986-05-13 Allied Corporation Amorphous alloys for electromagnetic devices
EP0175222A1 (en) * 1984-09-17 1986-03-26 Energy Conversion Devices, Inc. Method of preparing a hard magnet by addition of a quench rate range broadening additive and a hard magnet prepared thereby
US5160379A (en) * 1986-12-15 1992-11-03 Hitachi Metals, Ltd. Fe-base soft magnetic alloy and method of producing same
US5474624A (en) * 1992-09-14 1995-12-12 Alps Electric Co., Ltd. Method of manufacturing Fe-base soft magnetic alloy
US5619174A (en) * 1993-07-30 1997-04-08 Alps Electric Co., Ltd. Noise filter comprising a soft magnetic alloy ribbon core
US6187112B1 (en) 1995-04-13 2001-02-13 Ryusuke Hasegawa Metallic glass alloys for mechanically resonant marker surveillance systems
US5628840A (en) * 1995-04-13 1997-05-13 Alliedsignal Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
US6093261A (en) * 1995-04-13 2000-07-25 Alliedsignals Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
WO1996032518A1 (en) * 1995-04-13 1996-10-17 Alliedsignal Inc. Metallic glass alloys for mechanically resonant marker surveillance systems
EP1848837A2 (en) * 2005-02-11 2007-10-31 The Nanosteel Company Improved glass stability, glass forming ability, and microstructural refinement
EP1848837A4 (en) * 2005-02-11 2010-02-24 Nanosteel Co Improved glass stability, glass forming ability, and microstructural refinement
US7935198B2 (en) 2005-02-11 2011-05-03 The Nanosteel Company, Inc. Glass stability, glass forming ability, and microstructural refinement
US8704134B2 (en) 2005-02-11 2014-04-22 The Nanosteel Company, Inc. High hardness/high wear resistant iron based weld overlay materials
WO2012010940A2 (en) 2010-07-21 2012-01-26 Institut Polytechnique De Grenoble Amorphous metal alloy
WO2012010941A1 (en) 2010-07-21 2012-01-26 Rolex S.A. Watch-making or clock-making component comprising an amorphous metal alloy
WO2012010940A3 (en) * 2010-07-21 2012-11-01 Rolex S.A. Amorphous metal alloy
US9228625B2 (en) 2010-07-21 2016-01-05 Rolex S.A. Amorphous metal alloy
US9315884B2 (en) 2010-07-21 2016-04-19 Rolex Sa Watch-making or clock-making component comprising an amorphous metal alloy

Also Published As

Publication number Publication date
JPH04314846A (en) 1992-11-06
CA1222646A (en) 1987-06-09
DE3274562D1 (en) 1987-01-15
AU8433882A (en) 1983-02-24
KR840001228A (en) 1984-03-28
AU557318B2 (en) 1986-12-18
JPH0639663B2 (en) 1994-05-25
EP0072893B1 (en) 1986-12-03
KR870001283B1 (en) 1987-06-30

Similar Documents

Publication Publication Date Title
US4152144A (en) Metallic glasses having a combination of high permeability, low magnetostriction, low ac core loss and high thermal stability
US5252144A (en) Heat treatment process and soft magnetic alloys produced thereby
EP0574513B1 (en) PROCESS FOR THE PRODUCTION OF SOFT MAGNETIC ALLOYS ON THE BASIS OF Fe-Ni HAVING NANOCRYSTALLINE STRUCTURE
US5200002A (en) Amorphous low-retentivity alloy
EP0072893B1 (en) Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability
EP0430085B1 (en) Magnetic alloy with ultrafine crystal grains and method of producing same
US5370749A (en) Amorphous metal alloy strip
US4437907A (en) Amorphous alloy for use as a core
JPH044393B2 (en)
US6077367A (en) Method of production glassy alloy
JPS6133900B2 (en)
EP0240600B1 (en) Glassy metal alloys with perminvar characteristics
EP0119432B1 (en) Amorphous alloys for electromagnetic devices
JPS6362579B2 (en)
EP0088244B1 (en) Cobalt rich manganese containing near-zero magnetostrictive metallic glasses having high saturation induction
EP0084138B1 (en) Near-zero magnetostrictive glassy metal alloys with high magnetic and thermal stability
US4834814A (en) Metallic glasses having a combination of high permeability, low coercivity, low AC core loss, low exciting power and high thermal stability
JP3434844B2 (en) Low iron loss, high magnetic flux density amorphous alloy
US4473400A (en) Magnetic metallic glass alloy
JPH0351785B2 (en)
US4938267A (en) Glassy metal alloys with perminvar characteristics
US4743313A (en) Amorphous alloy for use in magnetic heads
EP0329704B1 (en) Near-zero magnetostrictive glassy metal alloys for high frequency applications
EP0121046B1 (en) Amorphous alloy for magnetic head and magnetic head with an amorphous alloy

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB IT NL SE

17P Request for examination filed

Effective date: 19830414

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL SE

REF Corresponds to:

Ref document number: 3274562

Country of ref document: DE

Date of ref document: 19870115

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
ITTA It: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 82104504.4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19990322

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19990406

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19990504

Year of fee payment: 18

Ref country code: FR

Payment date: 19990504

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19990531

Year of fee payment: 18

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000525

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20001201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20000524

EUG Se: european patent has lapsed

Ref document number: 82104504.4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010131

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20001201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST