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EP0160166A1 - Low magnetostriction amorphous metal alloys - Google Patents

Low magnetostriction amorphous metal alloys Download PDF

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Publication number
EP0160166A1
EP0160166A1 EP85101588A EP85101588A EP0160166A1 EP 0160166 A1 EP0160166 A1 EP 0160166A1 EP 85101588 A EP85101588 A EP 85101588A EP 85101588 A EP85101588 A EP 85101588A EP 0160166 A1 EP0160166 A1 EP 0160166A1
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ranges
magnetostriction
glasses
alloys
metal alloys
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German (de)
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Robert Charles O'handley
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Honeywell International Inc
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Allied Corp
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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

Definitions

  • This invention relates to amorphous metal alloys and, more particularly, to cobalt rich amorphous metal alloys that include certain transition metal and metalloid elements.
  • Metallic glasses generally show resistivities greater than 100.micro ohm cm, whereas crystalline and polycrystalline magnetic metals generally show resistivities below 50 micro ohm cm. Also, because of their randomly disordered structures, metallic glasses are typically -isotropic in their physical properties, including their magnetization. Because of these two characteristics, metallic glasses have an initial advantage over conventional magnetic metals. However, metallic glasses do not generally show zero magnetostriction. When zero magnetostriction glasses can be found they are generally good soft magnetic metals (R.C. O' Handley, B.A.
  • the present invention provides low magnetostriction and zero magnetostriction glassy alloys that are easy to fabricate and thermally stable.
  • the alloys are at least about 50 percent glassy and consist essentially of compositions defined by the formula:
  • a preferred magnetic alloy is one, wherein y ranges from about 0.3 to 0.6 or between 0.60 to 0.80 and z is respectively less than 0.2 or less than 0.15 when T is more than 50 percent of at least one of Cr and V, said alloy having a value of magnetostriction of about -6 x 10-6 to +4 x 10 -6 and a saturation induction of about 0.1 to 0.9T.
  • Special magnetic alloys according to the invention have a composition selected from the group consisting of Co 53.7 Ni 15.3 Fe 5.5 Mn 5.5 B 20 , Co 41 Ni 30 Fe 5 Mn 4 B 20 , Co 58 Ni 12 Fe 6 Mn 4 B 20 , Co 58 Ni 12 Fe 6 Mn 4 B 20 , Co 51 Ni 18 Fe 8 Cr 3 B 20 , Co 56 Ni 12 Fe 6 Cr 6 B 20' C040Ni30Fe5V5B20' Co 52 Ni 18 Fe 8 Mn 2 B 20 , Ni 45 Co 26.5 Fe 7.5 .Mn 1 B 20 , Co 39 Ni 30 Cr 6 Fe 5 B 20 , Co 51 Ni 18 Fe 9 Cr 2 B 20 and Co 59 Ni 12 Fe 6 V 5 B 20 .
  • the amorphous alloys of the invention can be formed by cooling a melt of the composition at a rate of at least about 10 5 °C/sec.
  • a variety of techniques are available, as is now well-known in the art, for fabricating splat- quenched foils and rapid-quenched continuous ribbons, wire, sheet, etc.
  • a particular composition is selected, powders of the requisite elements (or of materials that decompose to form the elements, such as nickel-borides, etc.) in the desired proportions are melted and homogenized, and the molten alloy is rapidly quenched either on a chill surface, such as a rotating cooled cylinder, or in a suitable fluid medium,. such as a chilled brine solution.
  • the amorphous alloys may be formed in air. However, superior mechanical properties are achieved by forming these amorphous alloys in a partial vacuum with absolute pressure less than about 5.5 cm of Hg, and preferably about 100 ⁇ m to 1 cm of Hg, as disclosed in U.S. Patent No. 4,154,283 to Ray et al.
  • the amorphous metal alloys are at least 50 percent amorphous, and preferably at least 80 per cent amorphous, as measured by X-ray diffraction. However, a substantial degree of amorphousness approaching 100 percent amorphous is obtained by forming these amorphous metal alloys in a partial vacuum. Ductility is thereby improved, and such alloys possessing a substantial degree of amorphousness are accordingly preferred.
  • Ribbons of these alloys find use in soft magnetic applications and an applications requiring low magnetostriction, high thermal stability (e.g., stable up to about 100°C) and excellent fabricability.
  • the magnetostriction measurements were made in fields up to 4 KOe with metal foil strain gauges (as reported in more detail by R.C. O'Handley in Solid State Communications, Vol. 22, p. 485, 1977). The accuracy of these measurements is considered to be within 10 per cent of full strain and their strain sensitivity is on the order of 10-7.
  • Co-rich glass compositions with positive and negative magnetostriction can be added linearly to give zero magnetostriction.
  • ⁇ s for Co 70 Fe 10 B 20 and Co 80 B 20 glasses are +4 and -4 x 10 , respectively.
  • Ni-rich glasses are more easily made and are more stable if the "late" transition metal Ni is balanced to a certain extent by an "early" TM, e.g., Mn, Cr, V.
  • TM e.g., Mn, Cr, V.
  • examples of such glasses include Ni 50 Mn 30 B 20 , Ni 60 Cr 20 B 20 , or Ni 70 V 10 B 20 .

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

Abstract

A magnetic alloy that is at least 50 percent glassy, having the formula (CO1-x-y-zFexNiyTz)100-b(B1-wMw)b where T is at least one of Mn, Cr, V, Ti, Mo, Nb and W, M is at least one of Si, P, C and Ge, B ist boron x ranges from about 0.05 to 0.25, y ranges from about 0.05 to 0.80, z ranges from about 0 to 0.25, b ranges from about 12 to 30 atom percent, w ranges up to 0.75 when M is Si or Ge and up to 0.5 when M is C or P, said alloy having a value of magnetostriction of about -7 x 10-6 and +5 x 10-6 and a saturation induction of about 0.2 to 1.4T.

Description

    BACKGROUND OF THE INVENTION 1. Field of the Invention
  • This invention relates to amorphous metal alloys and, more particularly, to cobalt rich amorphous metal alloys that include certain transition metal and metalloid elements.
    • 2. Description of the Prior Art
  • There are three physical parameters which can inhibit the easy magnetization and demagnetization of magnetic materials: strong anisotropy, non-zero magnetostriction and, at high frequencies, low resistivity. Metallic glasses generally show resistivities greater than 100.micro ohm cm, whereas crystalline and polycrystalline magnetic metals generally show resistivities below 50 micro ohm cm. Also, because of their randomly disordered structures, metallic glasses are typically -isotropic in their physical properties, including their magnetization. Because of these two characteristics, metallic glasses have an initial advantage over conventional magnetic metals. However, metallic glasses do not generally show zero magnetostriction. When zero magnetostriction glasses can be found they are generally good soft magnetic metals (R.C. O' Handley, B.A. Nesbitt, and L.I. Mendelsohn, IEEE Trans Mag-12, p. 942, 1976, U.S. Patents Nos. 4,038,073 and 4,150,981), because they satisfy the three approved criteria. For this reason, interest in zero magnetostriction glasses has been intense as indicated by the many publications on low magnetostriction metallic glasses (A.W. Simpson and W.G. Clements, IEEE Trans Mag-11, p. 1338, 1975; N. Tsuya, K.I. Arai, Y. -Shiraga and T. Masumoto, Phys. Lett. A51, p. 121, 1975; - H.A. Brooks, Jour. Appl. Phys. 47, p. 334, 1975; T. Egami, P.J. Flanders and C.D. Graham, Jr., Appl. Phys. Lett. 26, p. 128, 1975 and AIP Conf. Proc. No. 24, p. 697, 1975; R.C. Sherwood, E.M. Gyorgy, B.S. Chen, S.D. Ferris, G. Norman and H.J. Leamy, AIP Conf. Proc. No. 24, p. 745, 1975; H. Fujimori, K.I. Arai, H. Shiraga, M. Yamada, T. Masumoto and N. Tsuya, Japan, Jour. Appl. Phys. 15, p. 705, 1976; L. Kraus and J. Schneider, phys. stat. sol. a39, p. K161, 1977; R.C. O'Handley in Amorphous Magnetism, edited by R. Levy and R. Basegawa (Plenum Press, New York 1977), p. 379; R.C. O'Bandley, Solid State Communications 21, p. 1119, 1977; R.C. O'Handley, Solid State Communications 22, p. 458, 1977; R.C. O'Handley, Phys. Rev. 18, p. 930, 1978; H.S. Chen, E.M. Gyorgy, H.J. Leamy and R.C. Sherwood, U.S. Patent No. 4,056,411, Nov. 1, 1977).
  • The existence of a zero in the magnetostriction of Co-Mn-B glasses has been observed by H. Hilt- zinger of Vacuumschmeltze A.G., Hanau, Germany.
  • Reference to Co-rich glasses containing 6 atom percent of Cr is made by N. Heiman, R.D. Hempstead and N. Kazama in Journal of Applied Physics, Vol. 49, p. 5663,.1978. Their interest was in improving the corrosion resistance of Co-B thin films. No reference to magnetostriction is made in that article.
  • Saturation moments and Curie temperatures of Co80-xTxP10B10 glasses (T = Mn, Cr, or V) were recently reported by T. Mizoguchi in the Supplement to the Scientific Reports of RITU (Research Institutes of Tonoku University), A June 1978, p. 117. No reference to their magnetostrictive properties was reported.
  • In Journal of Applied Physics, Vol. 50, p. 7597, 1979, S. Ohnuma and T. Hasumoto outline their studies of magnetization and magnetostriction in Co-Fe-B-Si glasses with light transition metal (Mn, Cr, V, W, Ta, Mo and Nb) substitutions. They show that the coercivity decreases and the effective permeability increases in the composition range near zero magnetostriction.
  • New applications requiring improved soft zeromagnetic materials that are easily fabricated and have excellent stability have necessitated efforts to develop further specific compositions.
    • Summary of the Invention
  • The present invention provides low magnetostriction and zero magnetostriction glassy alloys that are easy to fabricate and thermally stable. The alloys are at least about 50 percent glassy and consist essentially of compositions defined by the formula:
    • (Co1-x-y-zFexNiyTz)100-b(B1-wMw)b' where T is at least one of Mn, Cr, V, Ti, Mo, Nb and W, M is at least one of Si, P, C and Ge, B is boron, x ranges from about 0.05 to 0.25, y ranges from about 0.05 to 0.80, z ranges from about 0 to 0.25, b ranges from about 12 to 30 atom percent , w ranges up to 0.75 when M is Si or Ge and up to 0.5 when M is C or P, said alloy having a value of magnetostriction of about -7 x 10-6 and +5 x 10-6 and a saturation induction of about 0.2 to 1.4T.
  • A preferred magnetic alloy is one, wherein y ranges from about 0.3 to 0.6 or between 0.60 to 0.80 and z is respectively less than 0.2 or less than 0.15 when T is more than 50 percent of at least one of Cr and V, said alloy having a value of magnetostriction of about -6 x 10-6 to +4 x 10-6 and a saturation induction of about 0.1 to 0.9T.
  • Special magnetic alloys according to the invention have a composition selected from the group consisting of Co53.7Ni15.3Fe5.5Mn5.5B20, Co41Ni30Fe5Mn4B20, Co58Ni12Fe6Mn4B20, Co58Ni12Fe6Mn4B20, Co51Ni18Fe8Cr3B20, Co56Ni12Fe6Cr6B20' C040Ni30Fe5V5B20' Co52Ni18Fe8Mn2B20, Ni45Co26.5Fe7.5.Mn1B20, Co39Ni30Cr6Fe5B20, Co51Ni18Fe9Cr2B20 and Co59Ni12Fe6V5B20.
  • The purity of the above composition is that found in normal commercial practice.
    • Brief Description of the Drawings
  • The invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed description of the preferred embodiments of the invention and the accompanying drawing, which is a triangular Fe-Co-Ni diagram showing regions of positive and negative magnetostriction, the dotted line isolating therefrom the region of nickel-rich compositions wherein amorphous metals are difficult to form and thermally unstable.
    • Description of the Preferred Embodiments
  • The amorphous alloys of the invention can be formed by cooling a melt of the composition at a rate of at least about 105°C/sec. A variety of techniques are available, as is now well-known in the art, for fabricating splat- quenched foils and rapid-quenched continuous ribbons, wire, sheet, etc. Typically, a particular composition is selected, powders of the requisite elements (or of materials that decompose to form the elements, such as nickel-borides, etc.) in the desired proportions are melted and homogenized, and the molten alloy is rapidly quenched either on a chill surface, such as a rotating cooled cylinder, or in a suitable fluid medium,. such as a chilled brine solution. The amorphous alloys may be formed in air. However, superior mechanical properties are achieved by forming these amorphous alloys in a partial vacuum with absolute pressure less than about 5.5 cm of Hg, and preferably about 100 µm to 1 cm of Hg, as disclosed in U.S. Patent No. 4,154,283 to Ray et al.
  • The amorphous metal alloys are at least 50 percent amorphous, and preferably at least 80 per cent amorphous, as measured by X-ray diffraction. However, a substantial degree of amorphousness approaching 100 percent amorphous is obtained by forming these amorphous metal alloys in a partial vacuum. Ductility is thereby improved, and such alloys possessing a substantial degree of amorphousness are accordingly preferred.
  • Ribbons of these alloys find use in soft magnetic applications and an applications requiring low magnetostriction, high thermal stability (e.g., stable up to about 100°C) and excellent fabricability.
  • The following example is presented to provide a more complete understanding of the invention.
    • Example
  • An alloy melt of known composition was rapidly quenched to form non-crystalline ribbons, presumably of the same composition as the melt. The ribbons, typically 40 micrometers (µm) by 2 mm in cross section, were cut into squares for vibration-sample magnetometer measurements of specific magnetization cr (4.2K, 9 Koe) and a (T, 9 KOe) with 295 K < T < Tx, the crystallization temperature. Curie temperatures were obtained from the inflection points in the σ (T, 9 KOe) curves.
  • The magnetostriction measurements were made in fields up to 4 KOe with metal foil strain gauges (as reported in more detail by R.C. O'Handley in Solid State Communications, Vol. 22, p. 485, 1977). The accuracy of these measurements is considered to be within 10 per cent of full strain and their strain sensitivity is on the order of 10-7.
  • Co-rich glass compositions with positive and negative magnetostriction can be added linearly to give zero magnetostriction. For example, λs for Co70Fe10B20 and Co80B20 glasses are +4 and -4 x 10 , respectively. A 50-50 per cent mixture of these glasses gives Co75 Fe5B20 which does in fact show λs = 0 (O'Handley et al., IEEE Trans Mag-12, p. 942, 1976). Similarly, for Co40Ni40B40λs = -7 x 10-6 while for Fe80B20λs = 32 x 10-6. A linear mixture having λ= 0 would be 0.18 x (Fe80B20) + 0.82 x (Co40Ni40B20) = Co38Ni33Fe14B20 which is very close to the observed λs = 0 composition, Co33.5Ni33.5Fe13B20.
  • The rule of linear combination of opposing magnetostrictions (LCOM) can be applied across the Co-Ni side of the Fe-Co-Ni triangular magnetostrictions diagram shown in the drawing (see also U.S. Patent No. 4,150,981 to O'Handley). Table I sets forth some typical near-zero magnetostriction compositions.
    Figure imgb0001
  • Referring to.the drawing, a region of difficult to fabricate and relatively unstable glasses exist in the Ni-rich corner of the triangular Fe-Co-Ni diagram. Yet, glassy alloys of zero or low magnetostriction exist there with potential for various applications.
  • Ni-rich glasses are more easily made and are more stable if the "late" transition metal Ni is balanced to a certain extent by an "early" TM, e.g., Mn, Cr, V. Examples of such glasses include Ni50Mn30B20, Ni60Cr20B20, or Ni70V10B20.
  • Based on the evidence of λs = 0 alloys set forth above and the known stabilizing effects of light TM's on Ni-rich glasses, new low magnetostriction glasses rich in Ni have been developed in the region below or near the λs = 0-line in the drawing (i.e., glasses initially showing λs < 0) by the addition of Mn, Cr, and/or V. Thus, for example, (Co.25Ni.75)80B20 can be rendered more fabricable and more stable in the glassy state, and its negative magnetostriction can be increased to near zero by substituting Mn, Cr or V for Co: (Ni.75Co.25-xTx)80B20.

Claims (3)

1. A magnetic alloy that is at least 50 percent glassy, having the formula (Co1-x-y-zFexNiyTz)100-b(B1-wMw)b, where T is at least one of Mn, Cr, V, Ti, Mo, Nb and W, M is at least one of Si, P, C and Ge, B ist boron, x ranges from about 0.05 to 0.25, y ranges from about 0.05 to 0.80, z ranges from about 0 to 0.25, b ranges from about 12 to 30 atom percent , w ranges up to 0.75 when M is Si or Ge and up to 0.5 when M is C or P, said alloy having a value of magnetostriction of about -7 x10-6 and +5 x 10-6 and a saturation induction of about 0.2 to 1.4T.
2. A magnetic alloy, as recited in claim 1, wherein y ranges from about 0.3 to 0.6 or between 0.60 to 0.80 and z is respectively less than 0.2 or less than 0.15 when T is more than 50 percent of at least one of Cr and V, said alloy having a value of magnetostriction of about -6 x 10-6 to +4 x 10-6 and a saturation induction of about 0.1 to 0.9T.
3. A magnetic alloy having a composition selected from the group consisting of Co53.7Ni15.3Fe5.5Mn5.5B20, Co41Ni30Fe5Mn4B20, Co58Ni12Fe6Mn4B20, Co51Ni18Fe8Cr3B20, Co56Ni12Fe6Cr6B20, Co40Ni30Fe5V5B20, Co52Ni18Fe8Mn2B20, Ni45Co26.5Fe7.5Mn1B20, Co39Ni30Cr6Fe5B20, Co51Ni18Fe9Cr2B20 and Co59Ni12Fe6V5B20.
EP85101588A 1981-11-26 1981-11-26 Low magnetostriction amorphous metal alloys Withdrawn EP0160166A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003699A1 (en) * 1986-11-03 1988-05-19 Allied Corporation Near-zero magnetostrictive glassy metal alloys for high frequency applications
GB2233345A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Ferromagnetic alloys with high nickel content and high permeability
US5037494A (en) * 1987-05-21 1991-08-06 Vacuumschmelze Gmbh Amorphous alloy for strip-shaped sensor elements
WO2022006978A1 (en) * 2020-07-10 2022-01-13 瑞声声学科技(深圳)有限公司 Low temperature assistant alloy powder, soft magnetic alloy and preparation method therefor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2553003A1 (en) * 1974-11-29 1976-08-12 Allied Chem MAGNETIC DEVICES
US4038073A (en) * 1976-03-01 1977-07-26 Allied Chemical Corporation Near-zero magnetostrictive glassy metal alloys with high saturation induction
US4056411A (en) * 1976-05-14 1977-11-01 Ho Sou Chen Method of making magnetic devices including amorphous alloys
US4081298A (en) * 1976-09-07 1978-03-28 Allied Chemical Corporation Heat treatment of iron-nickel-phosphorus-boron glassy metal alloys
US4150981A (en) * 1977-08-15 1979-04-24 Allied Chemical Corporation Glassy alloys containing cobalt, nickel and iron having near-zero magnetostriction and high saturation induction
DE2824749A1 (en) * 1978-06-06 1979-12-13 Vacuumschmelze Gmbh INDUCTIVE COMPONENT AND PROCESS FOR ITS MANUFACTURING
EP0021101A1 (en) * 1979-06-15 1981-01-07 Vacuumschmelze GmbH Amorphous soft magnetic alloy
US4288260A (en) * 1977-12-16 1981-09-08 Matsushita Electric Industrial Co. Ltd. Method of heat treatments of amorphous alloy ribbons

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2553003A1 (en) * 1974-11-29 1976-08-12 Allied Chem MAGNETIC DEVICES
US4038073A (en) * 1976-03-01 1977-07-26 Allied Chemical Corporation Near-zero magnetostrictive glassy metal alloys with high saturation induction
US4056411A (en) * 1976-05-14 1977-11-01 Ho Sou Chen Method of making magnetic devices including amorphous alloys
US4081298A (en) * 1976-09-07 1978-03-28 Allied Chemical Corporation Heat treatment of iron-nickel-phosphorus-boron glassy metal alloys
US4150981A (en) * 1977-08-15 1979-04-24 Allied Chemical Corporation Glassy alloys containing cobalt, nickel and iron having near-zero magnetostriction and high saturation induction
US4288260A (en) * 1977-12-16 1981-09-08 Matsushita Electric Industrial Co. Ltd. Method of heat treatments of amorphous alloy ribbons
DE2824749A1 (en) * 1978-06-06 1979-12-13 Vacuumschmelze Gmbh INDUCTIVE COMPONENT AND PROCESS FOR ITS MANUFACTURING
EP0021101A1 (en) * 1979-06-15 1981-01-07 Vacuumschmelze GmbH Amorphous soft magnetic alloy

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, unexamined applications, section C, vol. 2, no. 136, November 11, 1978 THE PATENT OFFICE JAPANESE GOVERNMENT page 2948 C 78 * JP - A - 53-102 219 ( TOKYO DENKI ) * *
PATENT ABSTRACTS OF JAPAN, unexamined applications, section C, vol. 2, no. 155, December 26, 1978 THE PATENT OFFICE JAPANESE GOVERNMENT page 3718 C 78 * JP - A - 53-120 625 (MATSUSHITA DENKI ) * *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003699A1 (en) * 1986-11-03 1988-05-19 Allied Corporation Near-zero magnetostrictive glassy metal alloys for high frequency applications
US5037494A (en) * 1987-05-21 1991-08-06 Vacuumschmelze Gmbh Amorphous alloy for strip-shaped sensor elements
GB2233345A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Ferromagnetic alloys with high nickel content and high permeability
GB2233345B (en) * 1989-06-29 1994-02-16 Pitney Bowes Inc Ferromagnetic alloys with high nickel content and high permeability
WO2022006978A1 (en) * 2020-07-10 2022-01-13 瑞声声学科技(深圳)有限公司 Low temperature assistant alloy powder, soft magnetic alloy and preparation method therefor

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