WO1988003699A1 - Alliages metalliques vitreux magnetostrictifs proches de zero pour applications haute frequence - Google Patents

Alliages metalliques vitreux magnetostrictifs proches de zero pour applications haute frequence Download PDF

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Publication number
WO1988003699A1
WO1988003699A1 PCT/US1987/002802 US8702802W WO8803699A1 WO 1988003699 A1 WO1988003699 A1 WO 1988003699A1 US 8702802 W US8702802 W US 8702802W WO 8803699 A1 WO8803699 A1 WO 8803699A1
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WO
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Prior art keywords
ranges
alloys
glassy
atom percent
formula
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Application number
PCT/US1987/002802
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English (en)
Inventor
Ryusuke Hasegawa
Original Assignee
Allied Corporation
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Application filed by Allied Corporation filed Critical Allied Corporation
Priority to DE8787907699T priority Critical patent/DE3775778D1/de
Priority to JP62507130A priority patent/JPH0625399B2/ja
Publication of WO1988003699A1 publication Critical patent/WO1988003699A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15316—Amorphous metallic alloys, e.g. glassy metals based on Co

Definitions

  • This invention relates to glassy metal alloys with near-zero magnetostriction which are especially suited for use in high frequency applications.
  • Saturation magnetostriction ⁇ s is related to the fractional change in length of ⁇ l/l that occurs in a magnetic material on going from the demagnetized to the saturated, ferromagnetic state.
  • the value of magnetostriction a dimensionless quantity, is often given in units of microstrains (i.e., a microstrain is a fractional change in length of one part per million).
  • Ferromagnetic alloys of low magnetostriction are desirable for several interrelated reasons: 1. Soft magnetic properties (low coercivity, high permeability) are generally obtained when both the saturation magnetostriction ⁇ s and the magnetocrystalline anisotropy K approach zero.
  • alloys of lower magnetostriction will show lower dc coercivities and higher permeabilities.
  • Such alloys are suitable for various soft magnetic applications.
  • Magnetic properties of such zero magnetostrictive materials are insensitive to mechanical strains. When this is the case, there is little need for stress-relief annealing after winding, punching or other physical handling needed to form a device from such material. In contrast, magnetic properties of stress-sensitive materials, such as the crystalline alloys, are seriously degraded by such cold working and such materials must be carefully annealed. 3.
  • the low dc coercivity of zero magnetostrictive materials carries over to ac operating conditions where again low coercivity and high permeability are realized (provided the magneto-crystalline anisotropy is not too large and the resistivity not too small).
  • zero magnetostrictive magnetic alloys (of moderate or low magnetocrystalline anisotropy) are useful where low loss and high ac permeability are required.
  • Such applications include a variety of tape-wound and laminated core devices, such as power transformers, signal transformers, magnetic recording heads and the like.
  • electromagnetic devices containing zero magnetostrictive materials generate no acoustic noise under AC excitation, while this is the reason for the lower core loss mentioned above, it is also a desirable characteristic in itself because it eliminates the hum inherent in many electromagnetic devices.
  • Nickel-iron alloys containing approximately 80% nickel (“80 nickel permalloys");
  • Zero magnetostrictive alloys based on the binaries but with small additions of other elements such as molybdenum, copper or aluminum to provide specific property changes. These include, for example, 4% Mo, 79% Ni, 17% Fe (sold under the designation Moly Permalloy) for increased resistivity and permeability; permalloy plus varying amounts of copper (sold under the designation Mumetal) for magnetic softness and improved ductility; and 85 wt. % Fe, 9 wt. % Si, 6 wt. % A1 (sold under the designation Sendust) for zero anisotropy.
  • the alloys included in category (1) are the most widely used of the three classes listed above because they combine zero magnetostriction with low anisotropy and are, therefore, extremely soft magnetically; that is they have a low coercivity, a high permeability and a low core loss. These permalloys are also relatively soft mechanically and their excellent magnetic properties, achieved by high temperature (above 1000°C) anneal, tend to be degraded by relatively mild mechanical shock.
  • Category (2) alloys such as those based on Co 90 Fe 10 have a much higher saturation induction (R s about 1.9 Tesla) than the permalloys. However, they also have a strong negative magnetocrystalline anisotropy, which prevents them from being good soft magnetic materials. For example, the initial permeability of Co 90 Fe 10 is only about 100 to 200.
  • Category (3) alloys such as Fe/6 wt% Si and the related ternary alloy Sendust (mentioned above) also show higher saturation inducations (B s about 1.8 Tesla and 1.1 Tesla, respectively) than the permalloys.
  • these alloys are extremely brittle and have, therefore, found limited use in powder form only.
  • compositional dependence of the magnetostriction is very strong in these materials, difficult precise tayloring of the alloy composition to achieve near-zero magnetostriction.
  • glassy metal alloys of zero magnetostriction. Such alloys might be found near the compositions listed above. Recause of the presence of metalloids which tend to quench the magnetization by the transfer of charge to the transition-metal d-electron states, however, glassy metal alloys based on the 80 nickel permalloys are either non-magnetic at room temperature or have unacceptably low saturation inductions.
  • the glassy alloy Fe 40 Ni 40 P 14 B 6 (the subscripts are in atom percent) has a saturation induction of about 0.8 Tesla, while the glassy alloy Ni 49 Fe 29 P 14 B 6 Si 2 has a saturation induction of about 0.46 Tesla and the glassy alloy Ni 80 P 20 is nonmagnetic.
  • No glassy metal alloys having a saturation magnetostriction approximately equal to zero have yet been found near the iron-rich Sendust composition.
  • a number of near-zero magnetostrictive glassy metal alloys based on the Co-Fe crystalline alloy mentioned above in (2) have been reported in the literature. These are, for example, Co 72 Fe 3 P 16 B 6 AL 3 (AIP Conference Proceedings, No. 24, pp. 745-746 (1975)) Co 70.5 Fe 4.5 Si 15 B 10 (Vol. 14, Japanese Journal of Applied Physics, pp. 1077-1078 (1975))
  • the saturation induction (B s ) of these alloys ranges between 0.6 and 1.2 Tesla.
  • the glassy .alloys with B s close to 0.6 T show low coercivities and high permeabilities comparable to crystalline supermalloys.
  • these alloys tend to be magnetically unstable at relatively low (150°C) temperatures.
  • the glassy alloys with B s ⁇ 1.2 Tesla tend to have their ferromagnetic Curie temperatures ( ⁇ f ) near or above their first crystallization temperatures (T cl ). This makes heat-treatment of these materials very difficult to achieve desired soft magnetic properties because such annealing is most effective when carried out at temperatures near ⁇ f .
  • a magnetic alloy that is at least 70% glassy, and which has a near-zero magnetostriction, high magnetic and thermal stability and excellent soft magnetic properties at high frequencies.
  • the glassy metal alloy has the composition CO a Fe b Ni c M d B e Si f , where subscripts are in atom percents and "a" ranges from about 65.5 to about 70.5, “h” ranges from about 3.8 to about 4.5, “c” ranges from about 0 to about 3, “d” ranges from about 1 to about 2, “e” ranges from about 10 to about 12 and “f” ranges from about 14 to about 15 when M is selected from a group consisting of vanadium, chromium, molybdenum, niobium and tungsten; when M is manganese, "a” ranges from about 68.0 to about 70.0, “b” ranges from about 2.5 to about 4.0, “c” ranges from about 0 to about 3, "d” ranges from about 1 to
  • the glassy alloy has a value of saturation magnetostriction ranging from about -1 x 10 -6 to + 1 x 10 -6 , a saturation induction ranging from about 0.65 to about 0.80 Tesla, a Curie temperature ranging from about 245 to about 310°C and the first crystallization temperature ranging from about 530 to 575°C.
  • a magnetic alloy that is at least 70% glassy and which has an outstanding combination of properties, including a near-zero magnetostriction, high magnetic and thermal stability and such soft magnetic properties as high permeability, low ac core loss and low coercivity.
  • the glassy metal alloy has the composition Co a Fe b Ni c M d B e Si f , where the subscripts are in atom percent and "a" ranges from about 65.5 to about 70.5, “b” ranges from about 3.8 to about 4.5, “c” ranges from about 0 to about 3, “d” ranges from about 1 and to about 2, “e” ranges from about 10 to about 12 and “f” ranges from about 14 to about 15 when M is selected from the group consisting of vanadium, chromium, molybdenum, niobium and tungsten; and when M is manganese, "a” ranges from about 68.0 to about 70.0, “b” ranges from about 2.5 to about 4.0, “c” ranges from about 0 to about 3, “d” ranges from about 1 to 4, “e” ranges from about 10 to about 12 and “f” ranges from about 14 to about 15.
  • the glassy alloy has a value of saturation magnetostriction ranging from about -1 x 10 -6 to about +1 x 10 -6 , a saturation induction ranging from about 0.65 to 0.80 Tesla, a Curie temperature ranging from about 245 to about 310°C and the first crystallization temperature ranging from about 530 to 575°C.
  • Examples of essentially zero magnetostrictive glassy metal alloys of the invention include.
  • the presence of the metal element M is to increase T cl and hence the thermal stability of the alloy system.
  • the glassy alloys of Table II exhibiting the saturation magnetostriction value ranging from -1 x 10 -6 to + 10 -6 may qualify.
  • the value of the magnetostriction is essentially determined by the ratio of Fe/(Co+Fe) or (Fe+Mn)/(Co+Fe+Mn). These ratios are about 0.06 and 0.07-0.09 respectively.
  • the small amount of the element Ni and the metal M excepting Mn which is present in the glassy alleys of the present invention is relatively ineffective to alter the magnetostriction of these alloys.
  • the glassy alloy of the invention are conveniently prepared by techniques readily available elsewhere; see, e.g., U.S. Patent 3,845,805, issued November 5, 1974 and 3,856,513, issued December 24, 1974.
  • the glassy alleys, in the form of continuous ribbon, wire, etc. are rapidly quenched from a melt of the desired composition at a rate of at least about 10 5 K/sec.
  • a metalloid content of boron and silicon in the range of about 24 to 27 atom percent of the total alloy composition is sufficient for glass formation, with boron ranging from about 10 to 12 atom percent and silicon ranging frcm about 14 to about 15 atom percent.
  • Tables III and IV give ac core loss (L) , exciting power (P 8 ) and permeabili ty ( ⁇ ) at 0.1 Tesla induction and at 50 kHz of the near-zero magnetostrictive glassy alloys of the present invention annealed at different temperature (T O ).
  • the advantageous combination of properties provided by the alloys of the present invention cannot be achieved in prior art nonmagnetostrictive glassy alloys with high saturation induction, such as Co 74 Fe 6 B 20 , because their Curie tetrperatures are higher than the first crystallization temperatures and the heat-treatment to improve their properties are not so effective as in those with lower saturation inductions.
  • the above properties, achieved in the glassy alleys of the present invention may be obtained in low induction glassy alloys of the prior art.
  • these alloys of the prior art such as Co 31.2 Fe 7 .8- Ni 39.0- R 14 Si 8 tend to be magnetically unstable at relatively low temperature of about 150°C as pointed out earlier.
  • Table V shows the magnetic properties of some of the representative glassy alloys of the composition Co a Fe b Ni c M d B e Si f (M is selected from the group consisting of V, Cr, Mn, Mo, Nb and W), in which at least one of a, b, c, d, e and f is outside the composition range defined in the present invention.
  • M is selected from the group consisting of V, Cr, Mn, Mo, Nb and W
  • the table indicates that the alloys with at least one of the constituents outside the defined ranges exhibit either Curie temperature or saturation induction too low to be practical in many magnetic applications
  • the ferromagnetic. Curie temperature ( ⁇ f ) was measured by inductance method and also monitored by differential scanning calorimetry, which was used primarily to determine the crystallization temperatures.
  • the first or primary crystallization temperature (T cl ) was used to compare the thermal stability of various glassy alloys of the present and prior art inventions.
  • Magnetic stability was determined from the reorientation kinetics of the magnetization, in accordance with the method described in Journal of Applied Physics, Vol. 49, p. 6510 (1978), which method is incorporated herein by reference thereto.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Power Engineering (AREA)
  • Soft Magnetic Materials (AREA)

Abstract

Un alliage métallique vitreux présente une valeur de magnétostriction proche de zéro et la composition CoaFebNicMdBeSif, où ''a'' est compris entre environ 65,5 et 70,5 % en atomes, ''b'' est compris entre 3,8 et 4,5 % en atomes, ''c'' est compris entre environ 0 et 3 % en atomes, ''d'' est compris entre environ 1 et 2 % en atomes, ''e'' est compris entre environ 10 et 12 % en atomes et ''f'' est compris entre environ 14 et 15 % en atomes lorsque M est sélectionné parmi le vanadium, le chrome, molybdène, niobium et tungstène; lorsque M est du manganèse, ''a'' est compris entre environ 68,0 et 70,0 % en atomes, ''b'' est compris entre environ 2,5 et 4,5 % en atomes, ''c'' est compris entre environ 0 et 3 % en atomes, ''d'' est compris entre environ 1 et 4 % en atomes, ''e'' est compris entre environ 10 et 12 % en atomes et ''f'' est compris entre environ 14 et 15 % en atomes. Cet alliage présente une valeur de magnétostriction de saturation comprise entre environ -1x10-6 et +1x10-6, une induction de saturation comprise entre environ 0,65 et environ 0,80 Tesla et un point de Curie compris entre environ 245 et 310°C.
PCT/US1987/002802 1986-11-03 1987-10-27 Alliages metalliques vitreux magnetostrictifs proches de zero pour applications haute frequence WO1988003699A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8787907699T DE3775778D1 (de) 1986-11-03 1987-10-27 Metallglasslegierungen mit sehr kleiner magnetostriktion fuer hochfrequenzanwendungen.
JP62507130A JPH0625399B2 (ja) 1986-11-03 1987-10-27 高周波使用のための磁歪がほぼ０のガラス質合金

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US92614786A 1986-11-03 1986-11-03
US926,147 1986-11-03

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2233346A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
EP0429022A2 (fr) * 1989-11-17 1991-05-29 Hitachi Metals, Ltd. Alliage magnétique contenant des grains de cristaux ultrafins et procédé de fabrication
EP0762354A1 (fr) * 1995-09-09 1997-03-12 Vacuumschmelze GmbH Corps allongés comme étiquette de sécurité pour des systèmes électromagnétiques antivol

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1114429B1 (fr) * 1998-09-17 2003-11-12 Vacuumschmelze GmbH Transformateur de courant a tolerance vis-a-vis du courant continu

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3021536A1 (de) * 1979-06-09 1980-12-18 Matsushita Electric Ind Co Ltd Amorphe massen mit verbesserten eigenschaften, insbesondere verbesserten magnetischen und kristallisationseigenschaften
EP0084138A2 (fr) * 1982-01-18 1983-07-27 Allied Corporation Alliages métalliques ayant une structure de verre, une magnétostriction de presque zéro et une grande stabilité magnétique et thermique
US4411716A (en) * 1980-07-11 1983-10-25 Hitachi, Ltd. Amorphous alloys for magnetic head core and video magnetic head using same
EP0160166A1 (fr) * 1981-11-26 1985-11-06 Allied Corporation Alliages de métal amorphes à magnétostriction basse

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5825449A (ja) * 1981-08-05 1983-02-15 Toshiba Corp 磁気ヘツド用非晶質磁性合金
JPS5985835A (ja) * 1982-11-10 1984-05-17 Toshiba Corp 高熱安定性、低保磁力、高角形性非晶質合金及びこの合金を用いた可飽和リアクトル
JPS61261451A (ja) * 1985-05-15 1986-11-19 Mitsubishi Electric Corp 磁性材料とその製造方法
JPS61210134A (ja) * 1985-11-16 1986-09-18 Res Inst Iron Steel Tohoku Univ 高透磁率で実効透磁率が大きく磁歪が小さく高硬度で耐摩耗性の大きい磁気ヘツド用非晶質合金の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3021536A1 (de) * 1979-06-09 1980-12-18 Matsushita Electric Ind Co Ltd Amorphe massen mit verbesserten eigenschaften, insbesondere verbesserten magnetischen und kristallisationseigenschaften
US4411716A (en) * 1980-07-11 1983-10-25 Hitachi, Ltd. Amorphous alloys for magnetic head core and video magnetic head using same
EP0160166A1 (fr) * 1981-11-26 1985-11-06 Allied Corporation Alliages de métal amorphes à magnétostriction basse
EP0084138A2 (fr) * 1982-01-18 1983-07-27 Allied Corporation Alliages métalliques ayant une structure de verre, une magnétostriction de presque zéro et une grande stabilité magnétique et thermique

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2233346A (en) * 1989-06-29 1991-01-09 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2264716A (en) * 1989-06-29 1993-09-08 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2233346B (en) * 1989-06-29 1993-12-22 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
GB2264716B (en) * 1989-06-29 1994-02-23 Pitney Bowes Inc Cobalt-niobium amorphous ferromagnetic alloys
EP0429022A2 (fr) * 1989-11-17 1991-05-29 Hitachi Metals, Ltd. Alliage magnétique contenant des grains de cristaux ultrafins et procédé de fabrication
EP0429022B1 (fr) * 1989-11-17 1994-10-26 Hitachi Metals, Ltd. Alliage magnétique contenant des grains de cristaux ultrafins et procédé de fabrication
EP0762354A1 (fr) * 1995-09-09 1997-03-12 Vacuumschmelze GmbH Corps allongés comme étiquette de sécurité pour des systèmes électromagnétiques antivol

Also Published As

Publication number Publication date
EP0329704A1 (fr) 1989-08-30
JP2697808B2 (ja) 1998-01-14
EP0329704B1 (fr) 1992-01-02
JPH0625399B2 (ja) 1994-04-06
JPH0693392A (ja) 1994-04-05
DE3775778D1 (de) 1992-02-13
JPH02500788A (ja) 1990-03-15

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