EP0254932B1 - Verfahren zum Wärmebehandeln von rasch abgeschreckten Fe-6,5% Si-Bändern - Google Patents

Verfahren zum Wärmebehandeln von rasch abgeschreckten Fe-6,5% Si-Bändern Download PDF

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Publication number
EP0254932B1
EP0254932B1 EP19870109970 EP87109970A EP0254932B1 EP 0254932 B1 EP0254932 B1 EP 0254932B1 EP 19870109970 EP19870109970 EP 19870109970 EP 87109970 A EP87109970 A EP 87109970A EP 0254932 B1 EP0254932 B1 EP 0254932B1
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EP
European Patent Office
Prior art keywords
ribbon
annealing
annealing step
domain
temperature
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.)
Expired
Application number
EP19870109970
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English (en)
French (fr)
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EP0254932A2 (de
EP0254932A3 (en
Inventor
Santosh Kumar Das
Chin-Fong Chang
Richard Lister Bye Jr.
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Honeywell International Inc
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AlliedSignal Inc
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Publication of EP0254932A3 publication Critical patent/EP0254932A3/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14766—Fe-Si based alloys
    • H01F1/14775—Fe-Si based alloys in the form of sheets
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/008—Heat treatment of ferrous alloys containing Si
    • 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
    • H01F1/15341—Preparation processes therefor

Definitions

  • This invention relates to a heat-treatment of rapidly quenched Fe-6 to 7, especially 6.5, wt% Si that, by controlling an order-disorder reaction, results in improved magnetic properties at high induction levels.
  • Fe-6.5 wt% Si alloy has extremely desirable ferromagnetic properties but has poor mechanical properties. It ordinarily has poor ductility and is not easily formed into thin ribbons or sheets that can be stamped or wound into selected shapes.
  • US-A-4 649 983 teaches a method of processing Fe-Si alloys containing 6 to 7 wt% Si to produce thin, ductile ribbon with improved magnetic properties. To produce the ribbon, a stream of molten alloy is ejected through a nozzle and rapidly quenched on the circumferential surface of a rapidly rotating disk, thereby forming a continuous sheet of alloy.
  • the as-cast ribbon is then vacuum annealed at temperatures ranging from 1000°C to 1200°C to obtain a columnar grain structure of a controlled size with a ⁇ 100> fiber texture.
  • the invention provides a method of heat treatment for rapidly quenched Fe-Si alloys containing 6 to 7 wt% Si which promotes an order-disorder reaction, thereby improving the magnetic properties at high induction levels, comprising the steps of: vacuum annealing at a temperature between 1000°C and 1200°C for 1 to 4 hours to develop ⁇ 100> texture with intensity at least 2 times random and a grain size of 1-2 mm; and annealing at a temperature of 500°C to 900°C for 1 to 4 hours and cooling at a rate sufficient to retain the annealed domain structure comprised of 100 to 850 nm B2 domains and 5 to 25 nm DO3 domains.
  • the ribbon is ductile enough so that it can be readily stamped, wound or otherwise formed into desired shapes. It has substantially isotropic ferromagnetic properties. These improved magnetic properties make the ribbon especially well suited for use in rotors and stators of electromagnetic devices such as motors and generators which operate at induction levels higher than 1.0 T.
  • a ribbon is a slender body whose transverse dimensions are much less than its length.
  • Such ribbon may be in the form of a ribbon, strip, or sheet, that is narrow or wide and of regular or irregular cross-section.
  • a ribbon is considered to be ductile if it can be bent around a radius of 10 times its thickness without fracture.
  • a texture in which all grains have a ⁇ 100> direction normal to the sheet surface and in all possible rotational positions about this normal) is most desirable in ferromagnetic materials in rotating equipment because the sheet then has isotropic ferromagnetic properties in its own plane.
  • a material is considered to have substantially isotropic ferromagnetic properties when its ferromagnetic properties, as determined by the B-H curve thereof, do not vary by more than 20% when measured in any direction within the plane of the ribbon.
  • Texture means the predominate orientation of the crystal grains within the metal when compared to a reference sample having randomly oriented grain crystals. Texture can be determined by conventional techniques, such as X-ray diffraction and electron diffraction analysis.
  • the present invention provides a method of processing as-cast ribbons of Fe-Si alloys containing 6 to 7 wt% Si to obtain optimum B2 and DO3 domain structures.
  • Ribbon processed by the method of this invention is ductile and has improved magnetic properties such as power loss and exciting power at high induction levels.
  • the ribbon is rapidly solidified and then processed by a two-step annealing process. In step (ii) the required cooling rates are readily achieved by furnace cooling in a hydrogen atmosphere.
  • the B2 domain size is approximately 160 nm and there is no evidence of DO3 domains.
  • Ac core losses and exciting power in these materials while attractive at induction levels below about 1.0 T, increase rapidly at higher induction levels.
  • both B2 and DO3 domains are present and ac core losses and exciting power are substantially improved at induction levels above approximately 1.2 T.
  • FIG. 1 A typical example of the B2 and DO3 domain structure in a Fe-6.5 wt% Si alloy subjected to the heat treatment of this invention is shown in Figure 1.
  • the domain size is strongly dependent on annealing temperature and only weakly dependent on annealing time.
  • Annealing at temperatures in the lower range of this invention 500°C to 700°C
  • a smaller domain size can be achieved by annealing at the higher temperatures of this invention (700°C to 900°C).
  • higher second step annealing temperatures and longer annealing times result in smaller B2 and DO3 domain sizes and in lower ac core losses and exciting power at high induction levels.
  • the second annealing step is carried out at a temperature between 790°C and 860°C.
  • Fe-Si ribbon annealed by this preferred procedure has a B2 domain size of 100-250 nm, a DO3 domain size of 5 to 10 nm, an ac core loss of 1.2 to 1.5 w/kg and an exciting power of 15 to 26 VA/kg, the ac core loss and exciting power being measured at an induction level of 1.4 T and a frequency of 60 Hz.
  • a strip of Fe-6.5 wt% Si alloy was cast using the planar flow casting process described in US-A-4,331,739.
  • the as-cast strip had a 100% columnar grain structure with an average grain size of 2.3 x 10 ⁇ 5m, and there were substantially no second phase particles at the grain boundaries.
  • the strip had a near random texture.
  • the material was annealed at 1100°C for 1 hour in vacuum to obtain the desired ⁇ 100> texture and optimum grain size.
  • Figure 2 shows representative micrographs of the grain size and grain morphology in a ribbon annealed at 1100°C for 1 hour. This annealed ribbon exhibits a strong ⁇ 100> texture with intensity as high as 44 times random, as shown in Figure 3.
  • the domain structure was observed in a Transmission Electron Microscope (TEM) dark field of the superlattice reflections corresponding to the B2 and DO3 structures.
  • TEM Transmission Electron Microscope
  • the size of B2 domains in the ribbon annealed at 1100°C for 1 hour is about 160 nm. No evidence of DO3 domains was found in this ribbon.
  • the magnetic properties (ac core loss and exciting power) of this annealed ribbon are shown in Table 1. These measurements were made by winding the samples, after heat treatment, with 100 turn primary and secondary windings. Core loss measurements were made with a Dranetz 3100 sampling network analyzer. Primary current was determined from the voltage across a 0.1 ohm noninductive resistor in the primary circuit. Resistive losses in the primary circuit were excluded by measuring the induced secondary voltage. The network analyzer sampled these voltage waveforms and calculated the total loss. Exciting power was calculated from rms voltmeter measurements on the same voltage waveforms.
  • a Hewlett Packard 9836 computer was utilized to control the network analyzer and frequency generator as well as to log data from them and from rms and average responding voltmeters via an IEEE 488 bus.
  • a computer program allowed the induction, as calculated from the average responding voltmeter, to be automatically set at preselected values and then all readings logged.
  • the computer calculated values for core loss and exciting power per kilogram. Voltage feedback from the secondary windings was necessary to maintain sinusoidal flux excitation due to the large exciting currents at high induction levels. Air-core flux compensators were also used due to these high exciting currents.
  • Samples of materials that had been cast and annealed as in Example 1 were given an additional annealing treatment at temperatures ranging from 500°C to 900°C for times ranging from 1 hour to 4 hours in a hydrogen atmosphere. After annealing, the furnace power was turned off and the sample allowed to cool to room temperature. Samples were prepared for microstructural analysis by TEM and for magnetic property measurement as described under Example 1. The following examples illustrate the effect of heat treatment on the domain size and magnetic properties of Fe-6.5 wt% Si ribbon.
  • the B2 and DO3 domain size, as determined from the TEM analysis, is listed in Table 2 for the different annealing temperatures and times.
  • Examples 2-10 illustrate that the order-disorder reaction in Fe-6.5 wt% Si, as reflected by the change of B2 and DO3 domain size, is strongly affected by the secondary annealing temperature, and relatively independent of annealing time.

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

Claims (10)

  1. Verfahren des Wärmebehandelns von rasch abgeschreckten Fe-Si Legierungen, welche 6 bis 7 Gewichts% Si enthalten, das eine Ordnungs/Unordnungs-Reaktion fördert und dadurch die magnetischen Eigenschaften bei hohen Induktionswerten verbessert, das folgende Schritte umfasst:
       Vakuum Ausglühung bei einer Temperatur zwischen 1000°C und 1200°C während 1 bis 4 Stunden, um eine <100> Textur mit einer zumindest zweifachen Zufallsintensität und einer Korngrösse von 1-2 mm; und
       Ausglühung bei einer Temperatur von 500°C bis 900°C während 1 bis 4 Stunden und Abkühlung mit einer Rate die ausreicht um die ausgeglühte Domänen-Struktur im Bereich von 100 bis 850 nm B2 Domäne und 5 bis 25 nm DO3 Domäne zu bewahren.
  2. Verfahren gemäss Anspruch 1, wobei der besagte Vakuum Ausglühungsschritt bei einer Temperatur zwischen 1075°C und 1125°C ausgeführt wird.
  3. Verfahren gemäss Anspruch 2, wobei der besagte zweite Ausglühungsschritt bei einer Temperatur zwischen 790°C und 860°C ausgeführt wird.
  4. Verfahren gemäss Ansprüchen 1, 2 oder 3, wobei der besagte zweite Ausglühungsschritt in einer Wasserstoff-Atmosphäre ausgeführt wird.
  5. Verfahren gemäss irgendeinem der Ansprüche 1 bis 4, wobei die besagte Abkühlung nach dem besagten zweiten Ausglühungsschritt in einer Wasserstoff-Atmosphäre ausgeführt wird.
  6. Verfahren gemäss irgendeinem der Ansprüche 1 bis 5, wobei die besagte Abkühlung nach dem besagten zweiten Ausglühungsschritt bei einer Rate von zwischen 15 und 35°C pro Minute erfolgt.
  7. Band, mit schlankem Körper und Querdimensionen, die viel weniger als dessen Länge ausmachen, aus einer Fe-Si Legierung, welche 6 bis 7 Gewichts% Si enthält, wobei das besagte Band:
    im wesentlichen eine <100> Textur mit zumindest zweifacher Zufallsintensität,
    eine Korngrösse von 1-2 mm,
    eine B2 Domänengrösse von 100 bis 850 nm,
    eine DO3 Domänengrösse von 5 bis 25 nm,
    einen Wechselstrom-Kernverlust von 1.2 bis 1.6 W/Kg bei einem Induktionswert von B=1.4 T und einer Frequenz von f=60 Hz, und
    eine Anregungsenergie von 15 bis 46 VA/Kg bei einem Induktionswert von B=1.4 T und einer Frequenz von f=60 Hz, aufweist.
  8. Band gemäss Anspruch 7, in welchem die besagte B2 Domänengrösse 100 bis 250 nm beträgt.
  9. Band gemäss Ansprüchen 7 oder 8, dessen besagter Wechselstrom-Kernverlust 1.2 bis 1.50 W/Kg, bei einem Induktionswert von B=1.4 T und einer Frequenz von f=60 Hz beträgt.
  10. Band gemäss Anspruch 7, 8 oder 9, dessen besagter Wechselstrom-Kernverlust bei einem Induktionswert von B=1.4 T und bei einer Frequenz von f=60 Hz 1.2 bis 1.50 W/Kg beträgt.
EP19870109970 1986-08-01 1987-07-10 Verfahren zum Wärmebehandeln von rasch abgeschreckten Fe-6,5% Si-Bändern Expired EP0254932B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US89413986A 1986-08-01 1986-08-01
US894139 1986-08-01

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EP0254932A2 EP0254932A2 (de) 1988-02-03
EP0254932A3 EP0254932A3 (en) 1989-07-19
EP0254932B1 true EP0254932B1 (de) 1992-10-21

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DE69312233T2 (de) * 1992-12-08 1997-12-18 Nippon Kokan Kk Elektroblech
CN112281060B (zh) * 2020-10-21 2022-07-01 江苏大磁纳米材料有限公司 一种封管加氢热处理退火工艺

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JPS55161057A (en) * 1979-06-04 1980-12-15 Sony Corp Manufacture of high permeability amorphous alloy
JPS5822331A (ja) * 1981-08-03 1983-02-09 Pioneer Electronic Corp 高透磁率合金薄帯の製造方法

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DE3782288T2 (de) 1993-03-04
JPS6353242A (ja) 1988-03-07
EP0254932A2 (de) 1988-02-03
JP2684177B2 (ja) 1997-12-03
EP0254932A3 (en) 1989-07-19
DE3782288D1 (de) 1992-11-26

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