EP0095831A2 - Amorphe Legierungen und daraus hergestellte Gegenstände - Google Patents

Amorphe Legierungen und daraus hergestellte Gegenstände Download PDF

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Publication number
EP0095831A2
EP0095831A2 EP83301712A EP83301712A EP0095831A2 EP 0095831 A2 EP0095831 A2 EP 0095831A2 EP 83301712 A EP83301712 A EP 83301712A EP 83301712 A EP83301712 A EP 83301712A EP 0095831 A2 EP0095831 A2 EP 0095831A2
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EP
European Patent Office
Prior art keywords
alloy
less
atomic percentages
boron
silicon
Prior art date
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Withdrawn
Application number
EP83301712A
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English (en)
French (fr)
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EP0095831A3 (de
Inventor
Stuart Leslie Ames
Thomas H. Gray
Lewis L. Kish
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.)
Allegheny Ludlum Steel Corp
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Allegheny Ludlum Steel Corp
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Publication date
Application filed by Allegheny Ludlum Steel Corp filed Critical Allegheny Ludlum Steel Corp
Publication of EP0095831A2 publication Critical patent/EP0095831A2/de
Publication of EP0095831A3 publication Critical patent/EP0095831A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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

  • This invention relates to amorphous metal alloys.
  • the invention relates to iron-boron-silicon amorphous metals and articles made thereof having improved magnetic properties and physical properties.
  • Amorphous metals may be made by rapidly solidifying alloys from their molten state to a solid state.
  • Various methods known in rapid solidification technology include spin casting and draw casting, among others.
  • Vapour and electrodeposition can also be used to make amorphous metals.
  • Amorphous metals provided by any of the above methods have distinctive properties associated with their non- crystalline structure. Such materials have been know, for example, to provide improved mechanical, electrical, magnetic and acoustical properties over counterpart metal alloys having crystalline structure.
  • the amorphous nature of the metal alloy can be determined by metallographic techniques or by X-ray diffraction. As used herein, an alloy is considered “amorphous" if the alloy is substantially amorphous, being at least 75% amorphous.
  • Best properties are obtained by having a (200) X-ray diffraction peak of less than 25.4mm (one inch) above the X-ray background level. This peak, in the case of body centered cubic ferrite (the hypoeutectic crystalline solid solution), occurs at a diffraction angle of 106 when using Cr K ⁇ radiation.
  • Luborsky discloses an iron-boron-silicon alloy with crystallization temperature (the temperature at which the amorphous metal reverts to its crystalline state) of at least 608°F (320 0 C), a coercivity of less than 0.03 oersteds, and a saturation magnetization of at least 174 emu/g (approximately 17,000 G).
  • the alloy contains 80 or more atomic percent iron, 10 or more atomic percent boron and no more than about 6 atomic percent silicon.
  • amorphous metal alloy strip greater than 1 - inch (2.54 cm) wide and less than 0.003-inch (.00762 cm) thick, having specific magnetic properties, and made of an alloy consisting essentially of 77-80% iron, 12-16% boron and 5-10% silicon, all atomic percentages, is disclosed in United States Patent application Serial No. 235,064, by the common Assignee of the present application.
  • United States Patent No. 4,217,135, DeCristofaro discloses an iron-boron-silicon alloy having 1.5 to 2.5 atomic percent carbon to enhance the magnetic properties.
  • an amorphous alloy and article are provided which overcome those problems of the known iron-boron-silicon amorphous metals.
  • An amorphous metal alloy is provided consisting of 73-80% iron, 4-10% boron and 14-17% silicon, by atomic percentages, and no more than incidental impurities. This alloy is lower in cost than either the other known amorphous alloys, or the commercially available Ni-Fe alloys which the alloy disclosed herein is designed to displace.
  • An article made from the amorphous metal alloy of the present invention is also provided, being at least singularly ductile (as herein defined) and having a core loss competitive with commercial Ni-Fe alloys, such as AL 4750, and particularly, a core loss of less than 0.163 watts per pound (WPP) at 12.6 kilogauss (1.26 tesla) at 60 Hertz.
  • the article of the alloy has a saturation magnetization measured at 75 oersteds (B 75H ) of at least 14.0 kilogauss (1.40 tesla) and a coercive force (H ) of less than 0.045 oersteds, and may be in the form of a thin strip or ribbon material product.
  • the alloy and resulting product have improved thermal stability characterized by a crystallization temperature (T ) of not less than 914°F (490°C).
  • the invention further provides a method of casting an amorphous strip material having a width of at least one inch (2.54cm), a thickness less than 0.003 inch (0.0762mm), a 60 Hertz core loss of less than 0.163 watts per pound at 12.6 kilogauss, saturation magnetization (B 75H ) of at least 14 kilogauss, a coercive force of less than 0.045 oersteds and is at least singularly ductile, comprising the steps of:
  • an amorphous alloy of the present invention consists essentially of 73-80% iron, 4-10% boron and 14-17% silicon.
  • the compositions lying inside the lettered area defining the relationships expressed by points A, B, C, D and E, are within the broad range of this invention.
  • the points A, F, G and H express relationships for compositions which lie within a preferred range of this invention.
  • the line between points I and J, crossing through and extending outside the composition area relationships herein defined, represents the locus of eutectic points (lowest melting temperatures) for the eutectic valley in this region of interest in the Fe-B-Si ternary diagram.
  • the Fe-B-Si composition ranges of the invention shown in Figure 1 are close enough to the eutectic line or trough to be substantially amorphous as cast.
  • the boron content is critical to the amorphousness of the alloy. The higher the boron content, the greater the tendency for the alloy to be amorphous. However, with increased boron content, the alloys become more costly.
  • the preferred boron range is from 4% to less than 10% and more preferably is 7% to less than 10%. Lower cost alloys of less than 7% boron are included in the invention, but are more difficult to cast with good properties.
  • Silicon in the alloy primarily affects the thermal stability of the alloy and to a small degree affects the amorphousness. Silicon has much less effect on the amorphousness of the alloy than does boron. Preferably, silicon may range from more than 15% to 17%.
  • the alloy of the present invention is rich in iron.
  • the iron contributes to the overall magnetic saturation of the alloy and preferably the iron content ranges from 73 to 78%.
  • the alloy composition of the present invention provides an optimization of the requisite properties of the Fe-B-Si alloys for certain electrical applications. Some properties have to be sacrificed at the expense of obtaining other properties, but the composition of the present invention is found to be an ideal balance between thbse properties. It has been found that the iron content does not have to exceed 80% to attain the requsite magnetic saturation. By keeping the iron content below 80%, the other major constituents, namely boron and especially silicon, can be provided in increased amounts. To obtain an article made of the alloy of the present invention having increased thermal stability, the silicon amount is maximized. Greater amounts of silicon raise the crystallization temperature, permitting the strip material to be heat treated at higher temperatures without causing crystallization. Being able to heat treat to higher temperatures is useful in releiving internal stresses in the article produced, which improves the magnetic properties. Also, higher crystallization temperatures extend the useful temperature range over which optimum magnetic properties are maintained for articles made therefrom.
  • incidental impurities In the alloy of the present invention, certain incidental impurities, or residuals, may be present. Such incidental impurities together should not exceed 0.83 atomic percent of the alloy composition. The following is a tabulation of typical residuals which can be tolerated in the alloys of the present invention.
  • a draw casting technique may include continuously delivering a molten stream or pool of metal through a slotted nozzle located within less than 0.025 inch (0.635mm) of a casting surface which may be moving at a rate of about 200 to 10,000 linear surface feet per minute (61 to 3048 m/minute ) past the nozzle to produce an amorphous strip material.
  • the casting surface is typically the outer peripheral surface of a water-cooled metal wheel made, for example, of copper. Rapid movement of the casting surface draws a continuous thin layer of the metal from the pool or puddle.
  • alloys of the present invention are cast at a temperature above about 2400°F (1315°C) onto a casting surface having an initial temperature that may range from about 35 to 90 0 F (1.6 to 32°C).
  • the strip is quenched to below solidification temperature and to below the crystallization temperature and after being solidified on the casting surface it is separated therefrom.
  • such strip may have a width of 1 inch (2.54 cm) or more and a thickness of less than 0.003 inch (0.0762mm), and a ratio of width-to-thickness of at least 10:1 and preferably at least 250:1.
  • each strip was annealed in a 10 oersted DC magnetic field for four hours at 662 0 F (350 0 C).
  • the amorphous character of each was confirmed by X-ray diffraction measurements.
  • each was found to have at least singular ductility as determined by a simple bend test.
  • Ductility determined by bend tests include bending the strip transversely upon itself in a 180 bend in either direction to determine the brittleness. If the strip can be bent upon itself along a bend line extending across the strip (i.e., perpendicular to the casting direction) into a non-recoverable permanent bend without fracturing, then the strip exhibits ductility.
  • the strip is double ductile if it can be bent 180° in both directions without fracture and single or singularly ducitile if it bends 18 0 0 only in one direction without fracture. Singular ductility is a minium requirement for an article made of the alloy of the present invention. Double ductility is an optimum condition for an article made of the alloy of the present invention.
  • the data of Table II (shown Below) demonstrates that the core loss, which should be as low as possible, of the alloy of the present invention is consistently less than the core loss of 0.163 WPP at 12.6 KG (1.26T) for a commercial alloy AL 4750 which nominally comprises 48% Ni-52% Fe.
  • the AL 4750 alloy tested was 0.006-inch (0.015cm) thick and was prepared in accordance with recognized commercial practice for the alloy.
  • the strips of the alloy of the present invention were about .0013-inch (.0033cm) thick.
  • the magnetic data for Heat No. 158 is inconsistent with the other alloy data for the reason that the (200) X-ray diffraction peak is slightly larger than the 1.0" (2.54cm) max. above background level established for best properties.
  • Heat 671 of the same composition was cast at a later date when casting techniques had improved allowing the alloy to be substantially amorphous by virtue of improved casting quench rate.
  • the properties of Heat 158 demonstrate the capability of the alloy composition in providing magnetic saturation of the level required and useful articles made therefrom.
  • an alloy composition which is outside out invention, Fe 73 B 7 si 20' Heat 621 having an extremely high silicon level, is still crystalline to a large extent and brittle when cast even under the best quenching conditions. Because the alloy is not substantially amorphous, it does not develop the desirable magnetic properties.
  • All of the heats, except ALR 621, are alloy compositions of the present invention.
  • the data shown in Table II demonstrates that the alloys of the present invention have magnetic properties of magnetic saturation, coercive force, core loss (in WPP) and apparent core loss (in voltamperes per pound, VAPP) comparable to or better than the AL 4750 alloy.
  • the present invention provides alloys useful for electrical applications and articles made from these alloys having good magnetic properties.
  • the alloys can be made less expensively because of the lower raw materials cost of boron.
  • the alloys are amorphous and ductile and have a thermal stability greater than those iron-boron-silicon alloys having more than 10 atomic percent boron and less than 14 atomic percent silicon.

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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)
  • Continuous Casting (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
EP83301712A 1982-05-27 1983-03-28 Amorphe Legierungen und daraus hergestellte Gegenstände Withdrawn EP0095831A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38282482A 1982-05-27 1982-05-27
US382824 1982-05-27

Publications (2)

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EP0095831A2 true EP0095831A2 (de) 1983-12-07
EP0095831A3 EP0095831A3 (de) 1984-06-27

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Family Applications (1)

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EP83301712A Withdrawn EP0095831A3 (de) 1982-05-27 1983-03-28 Amorphe Legierungen und daraus hergestellte Gegenstände

Country Status (10)

Country Link
EP (1) EP0095831A3 (de)
JP (1) JPS58210150A (de)
KR (1) KR840003296A (de)
AU (1) AU9179282A (de)
BR (1) BR8207585A (de)
CA (1) CA1195863A (de)
ES (1) ES520109A0 (de)
NO (1) NO830120L (de)
PL (1) PL242230A1 (de)
RO (1) RO86181B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177669A2 (de) * 1984-05-23 1986-04-16 AlliedSignal Inc. Amorphe Metallegierungen mit magnetischen Eigenschaften in Wechselstrom bei hohen Temperaturen
CN106636984A (zh) * 2017-01-25 2017-05-10 青岛云路先进材料技术有限公司 一种铁基非晶合金
CN106702291A (zh) * 2017-01-25 2017-05-24 青岛云路先进材料技术有限公司 一种铁基非晶合金及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211536A1 (de) * 1972-12-26 1974-07-19 Allied Chem
FR2423548A1 (fr) * 1978-04-20 1979-11-16 Gen Electric Alliages de fer-silicium amorphes
US4217135A (en) * 1979-05-04 1980-08-12 General Electric Company Iron-boron-silicon ternary amorphous alloys
EP0020937A1 (de) * 1979-05-25 1981-01-07 Allied Corporation Verfahren zur Verbesserung der magnetischen Eigenschaften von amorphen Metallegierungen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2038358B (en) * 1978-11-29 1982-12-08 Gen Electric Amorphous fe-b-si alloys
JPS56127749A (en) * 1980-03-12 1981-10-06 Nippon Steel Corp Amorphous thin alloy strip
JPS6034620B2 (ja) * 1981-03-06 1985-08-09 新日本製鐵株式会社 鉄損が極めて低く熱的安定性とよい非晶質合金

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2211536A1 (de) * 1972-12-26 1974-07-19 Allied Chem
FR2423548A1 (fr) * 1978-04-20 1979-11-16 Gen Electric Alliages de fer-silicium amorphes
US4217135A (en) * 1979-05-04 1980-08-12 General Electric Company Iron-boron-silicon ternary amorphous alloys
EP0020937A1 (de) * 1979-05-25 1981-01-07 Allied Corporation Verfahren zur Verbesserung der magnetischen Eigenschaften von amorphen Metallegierungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED PHYSICS, vol. 50, no. 3, part 11, March 1979, pages 1754-1756, American Institute of Physics, New York, US *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0177669A2 (de) * 1984-05-23 1986-04-16 AlliedSignal Inc. Amorphe Metallegierungen mit magnetischen Eigenschaften in Wechselstrom bei hohen Temperaturen
EP0177669A3 (en) * 1984-05-23 1987-04-22 Allied Corporation Amorphous metal alloys having enhanced ac magnetic properties at elevated temperatures
CN106636984A (zh) * 2017-01-25 2017-05-10 青岛云路先进材料技术有限公司 一种铁基非晶合金
CN106702291A (zh) * 2017-01-25 2017-05-24 青岛云路先进材料技术有限公司 一种铁基非晶合金及其制备方法

Also Published As

Publication number Publication date
JPS58210150A (ja) 1983-12-07
BR8207585A (pt) 1984-04-17
PL242230A1 (en) 1984-02-13
NO830120L (no) 1983-11-28
ES8500340A1 (es) 1984-10-01
EP0095831A3 (de) 1984-06-27
RO86181B (ro) 1985-03-31
AU9179282A (en) 1983-12-01
RO86181A (ro) 1985-03-15
ES520109A0 (es) 1984-10-01
KR840003296A (ko) 1984-08-20
CA1195863A (en) 1985-10-29

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