EP0513385A1 - Weichmagnetlegierung auf eisen-basis - Google Patents

Weichmagnetlegierung auf eisen-basis Download PDF

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EP0513385A1
EP0513385A1 EP91920808A EP91920808A EP0513385A1 EP 0513385 A1 EP0513385 A1 EP 0513385A1 EP 91920808 A EP91920808 A EP 91920808A EP 91920808 A EP91920808 A EP 91920808A EP 0513385 A1 EP0513385 A1 EP 0513385A1
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alloy
soft magnetic
magnetic
heat
base soft
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EP0513385A4 (en
EP0513385B1 (de
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Hiroshi Mitsui Petrochemical Ind. Ltd. Watanabe
Hitoshi Mitsui Petrochemical Ind. Ltd. Saito
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Mitsui Chemicals Inc
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Mitsui Petrochemical Industries Ltd
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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
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15308—Amorphous metallic alloys, e.g. glassy metals based on Fe/Ni
    • 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
    • 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
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to an Fe-base soft magnetic alloy and, in particular, to an alloy having excellent soft magnetic properties.
  • Fe-base amorphous magnetic alloys having a high saturation magnetic flux density are known to be used as magnetic core materials for high frequency transformers, saturable reactors, choke coils, etc.
  • Fe-base amorphous magnetic alloys are lower priced than Co-base ones, the former have the drawbacks of high saturation magnetostriction and core loss and a low permeability.
  • a method of producing an Fe-base amorphous alloy has been reported recently in which a thin Fe-base amorphous ribbonformed by rapidly quenching an alloy composition melt is heat-treated to generate fine crystalline particles having a particle size of about 100 ⁇ or so.
  • the Fe-base amorphous alloy thus produced exhibits better soft magnetic properties than any other conventional Fe-base amorphous alloys (Japanese Patent Application Laid-Open No. 64-79342, Japanese Patent Application Laid-Open No. Hei1-156452, U.S.P. 4,881,989).
  • the reported Fe-base amorphous alloy has a basic composition of FeSiB and additionally contains high melting point metals such as Cu, Nb, etc., in which the alloy structure has been finely crystallized to obtain fine crystalline particles having a particle size of about 100 ⁇ or so. Accordingly, the Fe-base amorphous alloy has become possible to have a lowered saturation magnetostriction, though conventional Fe-base amorphous alloys were difficult to have it. As a result, the reported Fe-base amorphous alloy is said to have improved soft magnetic properties, especially improved frequency characteristics of magnetic permeability.
  • One object of the present invention is to provide a novel Fe-base soft magnetic alloy, which is a soft magnetic material substitutable for the above-mentioned conventional soft magnetic materials and which has an extremely low saturation magnetostriction with having excellent high frequency magnetic properties, in particular, having a high permeability and a low iron loss in a high frequency region.
  • Another object of the present invention is to provide a Fe-base soft magnetic alloy which is a metal-metalloid alloy having a relatively low melting point and which can be produced by the use of any conventional device for producing ordinary magnetic materials.
  • an Fe-base soft magnetic alloy which has a composition represented by the formula: (Fe 1-x M x ) 100-a-b-c-d Si a Al b B c M' d where M is Co and/or Ni; M' is at least one element selected from the group consisting of Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C and P; x is an atomic ratio; a, b, c and d each are an atomic %; and x, a, b, c and d each satisfy 0 ⁇ x ⁇ 0.15, 0 ⁇ a ⁇ 24, 2 ⁇ b ⁇ 15, 4 ⁇ c ⁇ 20, and 0 ⁇ d ⁇ 10.
  • at least 30 % of the alloy structure is desired to be occupied by a crystalline phase (fine crystalline particles), and the crystalline phase is desired to be composed
  • the Fe-base soft magnetic alloys of the present invetnion contain less than 0.5, preferably less than 0.1 atomic % copper (Cu) and more preferably entirely free of copper in view of magnetic properties.
  • the Ni (and/or Co) content (x) is 0.02 ⁇ x ⁇ 0.15
  • such effect is obtained that the magnetostriction constant and a magnetocrystalline anisotropy constant of the alloy are reduced as noted previously, accompanied with the effect that the alloy has a high permeability.
  • a magnetocrystalline anisotropy is sufficiently induced in the alloy by heat treatment in a magnetic field.
  • the alloy is preferably applied to such a use as (material for magnetic core of) common-mode choke coil, an inductance coil for filters, transformers for signals, a high frequency transformer, a magnetic amplifier and so on.
  • the Ni (and/or Co) content (x) is preferably 0.02 ⁇ x ⁇ 0.15, and more preferably 0.03 ⁇ x ⁇ 0.1.
  • Al is an essential element of constituting the alloy of the present invention, and addition of a determined amount (more than 2 and not more than 15 atomic %) of Al to the alloy causes enlargement of the temperature difference ( ⁇ T) between the crystallization temperature (TX1) of the soft magnetic crystals having a small magnetocrystalline anisotropy (Fe-base bcc solid solution) and the crystallization temperature (TX2) of the crystals of interfering with the soft magnetic property (for example, Fe-B crystals) to thereby inhibit formation of Fe-B crystals in heat-treatment of the alloy composition and lead the resulting alloy to having sufficient soft magnetic properties by heat-treatment at a relatively low temperature.
  • ⁇ T the temperature difference between the crystallization temperature (TX1) of the soft magnetic crystals having a small magnetocrystalline anisotropy (Fe-base bcc solid solution) and the crystallization temperature (TX2) of the crystals of interfering with the soft magnetic property (for example, Fe-B crystals) to thereby inhibit formation of
  • FIG. 1 shows the relationship between the crystallization temperature of an Fe-base soft magnetic alloy to which Al is added and the Al content atomic % in the alloy. From Fig. 1, it is noted that increase of the Al content in the alloy causes simple decrease of TX1 while TX2 is relatively unchanged irrespective of the variation of the Al content, so that the increase of the Al content in the alloy thereby causes increase of the temperature difference ( ⁇ T) between TX1 and TX2.
  • the Al content (b) in the alloy is more than 2 atomic % and not more than 15 atomic %, preferably from 2.5 atomic % to 15 atomic % and more preferably from 3 to 12 atomic %. Determination of the Al content in the range 3 to 12 atomic % causes a high permeability and a low core loss.
  • the Al content (b) is preferably from 6 to 12 atomic %, more preferably from 6 to 10 atomic %, and most preferbly from 7 to 10 atomic %.
  • Si and B are elements which make the Fe-base soft magnetic alloy of the present invention amorphous in the initial stage (before heat-treatment).
  • the Si content in the alloy of the present invention is from 0 to 24 atomic %, preferably from 6 to 18 atomic %, and more preferably from 10 to 16 atomic %. Determination of the Si content in the said range preferably causes improvement of the ability of formation of amorphous in the initial stage (before the heat-treatment).
  • the B content (c) in the alloy of the present invention is from 4 to 20 atomic %, preferably from 6 to 15 atomic %, and more preferably from 10 to 14 atomic %.
  • a sufficient temperature difference between the crystallization temperatures (TX1 and TX2) can be obtained and the alloy may be made amorphous with ease.
  • the ability of formation of amorphous changes acccording to whether the content of B is more or less than 9 atomic %.
  • the amorphous alloy including Al is provided an excellent ability of amorphous formation and uniformalized crystal grains are obtained after heat treatment.
  • the basic composition of the Fe-base soft magnetic alloy of the present invention is composed of the above-mentioned Fe (M), B, Si and Al.
  • M Fe
  • other element(s) M' may be added to the alloy.
  • M' is mentioned at least one, i.e. one or more of the elements selected from the group consisting of Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Y, Pd, Ru, Ga, Ge, C and P. Addition of the M' elements is effective for improving the ability of the base composition of Fe-Si-Al-B alloy of forming the amorphous phase of the alloy.
  • the Nb, W, Ta, Zr, Hf, Ti and Mo elements are particularly effective to prevent crystallization of the Fe-B crystalline which hampers the soft magnetic properties of the alloy or to elevate it's crystallization temperature, whereby it improves the soft magnetic properties of the alloy. Further, addition of these elements to the alloy makes the crystal grain fine.
  • the V, Cr, Mn, Y and Ru elements are particularly effective in improving the anti-corrosion properties of the alloy.
  • the C, Ge, P and Ga elements are particularly effective in the process of forming the amorphous alloy. One more of the foregoing elements can be added.
  • these elements M' preferred are Nb, Ta, W, Mn, Mo and V. Above all, Nb is most preferred.
  • the content of the M' element(s) is from 1 to 10 atomic %, preferably from 1 to 8 atomic %, more preferably from 1 to 6 atomic %. Addition of the M' element(s) to the alloy of the present invention in such an amount as falling within the determined range forms in the alloy compound(s) of the added element(s) which may retard deterioration of the amorphous phase-forming ability and the magnetic properties of the alloy.
  • alloy further containing inevitable impurities such as N, S, O etc., is also comprised in the alloy composition of the presnet invention.
  • the Fe-base soft magnetic alloy according to the present invention has an alloy structure, at least 30 % of which consists of crystal (fine crystalline particles), with the balance of the structure being an amorphous phase.
  • the range of the ratio of the fine crystalline particles in the structure provides the alloy excellent (soft) magnetic properties.
  • the alloy has yet sufficiently good magnetic properties.
  • Preferably at least 60 %, more preferably 80 % or more of the alloy structure consists of the fine crystalline particles in view of magnetic properties.
  • the crystalline particles of the alloy of the present invention has a bcc structure, where Fe as a main component and Si, B, Al (occasionally Ni and/or Co) are dissolved in.
  • the crystalline particles to be formed in the alloy of the present invention have a particle size of 1000 ⁇ or less, preferably 500 ⁇ or less, more preferably 50 to 300 ⁇ .
  • the particle size being 1000 ⁇ or less, provides the alloy of the present invention excellent magnetic properties.
  • the proportion of the crystalline grains to the total alloy structure in the alloy of the present invention may be determined experimentally by an X-ray diffraction method of the like. Briefly, on the basis of the standard value of the X-ray diffraction intensity of the completely crystallized condition (saturated X-ray diffraction intensity condition), the proportion of the X-ray diffraction intensity of the magnetic alloy material sample to be examined to the standard value may be obtained experimentally.
  • the Fe-base soft magnetic alloy of the present invention may be produced by a rapid melt-quenching method of forming an amorphous metal from a melt of the above-mentioned composition.
  • an amorphous alloy is first formed in the form of a ribbon, powder or thin film by a single roll method, cavitation method, sputtering method or vapor deposition method, the resulting amorphous alloy is optionally shaped and worked into a desired shape, then it is heat-treated so that at least a part, preferably 30 % or more of the whole, of the sample is crystallized to obtain the alloy of the present invention.
  • a rapid-quenched alloy ribbon is formed by a single roll method, and this is shaped into a determined shape such as a coiled magnetic core and then heat-treated.
  • the heat-treatment is effected in vacuum, in an inert gas atmosphere, such as an argon gas or nitrogen gas atmosphere, in reducing gas atmosphere such as H2 or in oxidizing gas atmosphere such as air, after fully de-aired into vacuum.
  • an inert gas atmosphere such as an argon gas or nitrogen gas atmosphere
  • reducing gas atmosphere such as H2
  • oxidizing gas atmosphere such as air
  • the heat-treatment temperature is approximately from 200 to 800°C, preferably approximately from 400 to 700°C, and more preferably from 520 to 680 °C.
  • the heat-treatment time is desired to be from 0.1 to 10 hours, preferably from 1 to 5 hours.
  • the heat-treatment may be effected either in the absence or presence of a magnetic field.
  • the soft magnetic alloy having excellent propertiers is obtained.
  • Fig. 1 is a graph showing a relationship between the crystallization temperature of an Fe-base soft magnetic alloy and the Al content therein.
  • Fig. 2 is a graph showing a relationship between the coercive force (Hc) of an Fe-base soft magnetic alloy and the composition thereof.
  • Fig. 3 is a graph showing a relationship between the saturation magnetization (Ms) of an Fe-base soft magnetic alloy and the composition thereof.
  • Fig. 4 is a graph showing X-ray diffraction patterns of the Fe base soft magnetic amorphous alloy, and the cristalline alloy of the present invention.
  • Fig. 5 is a graph showing the temperature dependence of the magnetic flux density and the coercive force of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 6 is a graph showing the temperature dependence of the effective magnetic permeability of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 7 is a graph showing the temperature dependence of the iron loss of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 8 is a graph showing the temperature dependence of the crystal particle size and the lattice constant of a bcc crystal of an Fe base soft magnetic alloy of the present invention.
  • Fig. 9 is a graph showing the temperature dependence of the saturation magnetostriction of an Fe base soft magnetic alloy of the present invention.
  • Fig. 10 is a graph showing the frequency characteristic of the effective magnetic permeability of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 11 is a graph showing the frequency characteristic of the iron loss of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 12 is a graph showing the magnetic flux density dependence of the iron loss of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 13 is a graph showing the frequency characteristic of the effective magnetic permeability of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 14 is a graph showing the frequency characteristic of the iron loss of a magnetic core of an Fe base soft magnetic alloy of the present invention.
  • Fig. 15 is a graph showing B-H loop of an Fe base soft magnetic alloy of the present invention before heat-treatment.
  • Fig. 16 is a graph showing B-H loop of an Fe base soft magnetic alloy of the present invention after heat-treatment.
  • Fig. 17 is a graph showing X-ray diffraction patterns of the Fe base soft magnetic amorphous alloy, and the cristalline alloy of the present invention.
  • a quenched ribbon sample having a width of about 1.0-5 mm and a thickness of about 14-20 ⁇ m was formed from a melt containing Fe, Si, Al, B and (Nb)in an argon gas atmosphere of one atmosphere pressure by a single roll method. The sample was then heat-treated for about one hour in the presence of a nitrogen gas and argon gas in the absence of a magnetic field.
  • the iron loss of each of the thus heat-treated coiled magnetic core samples was determined from an area as surrounded by the alternating current hysteresis loop measured with a digital oscilloscope under the condition of a frequency of 100 kHz and a maximum magnetic flux density of 0.1 T.
  • the permeability ( ⁇ ) of each of them was determined by measuring the inductance L with an LCR meter under the condition of a frequency of 100 kHz and an exciting magnetic field of 5 mOe. The results obtained are also shown in Table 1 below.
  • Fe78Si9B13 (Comparative Example 1, commercial product) and FeCuSiBNb (Comparative Example 2, Cu-containing Fe-base soft magnetic alloy described in Japanese Patent Application Laid-Open No. 64-79342) were prepared, and the coercive force, saturation magnetization, iron loss and permeability of these samples were also shown in Table 1 below.
  • Example 7 containing Nb as M' had a much lower coercive force value than the other FeSiB samples.
  • the value of the coercive force of the sample of Example 7 is almost same as that of the sample of Comparative Example 2 (15 mOe).
  • the samples of Examples 3 and 4 had magnetic properties, with the exception of permeability and saturation magnetization, comparable or superior to those of FeSiB amorphous alloys of comparative Examples 1 and 2.
  • Example 9 had superior magnetic properties as to permeability, iron loss and magnetostriction than those of Comparative Example 1 and 2.
  • Fig. 2 is a graph showing the composition dependence of the coercive force Hc of various Fe-Si-Al-B alloy samples, in which the compositions as surrounded by the line gave a good soft magnetic characteristic of having a coercive force of not more than 100 mOe.
  • Fig. 3 is a graph showing the composition dependence of the saturation magnetization Ms of various Fe-Si-Al-B alloy samples, in which a sample (Fe73Si8Al10B9) having a high saturation magnetization of 165 emu/g was obtained from the composition range having a coercive force Hc of not higher than 100 mOe.
  • Example 4 the sample of Example 4 (Fe69Al8Si14B9) and the sample of Example 7 (Fe68Al8Si14B9Nb1) having a smaller coercive force than the conventional FeSiB amorphous alloy sample (Comparative Example 1) were measured with respect to the crystal constant a (A), the crystal particle size D (A), the first crystallization temperature TX1 (°C) and the second crystallization temperature TX2 (°C). The data measured are shown in Table 2 below. Table 2 TX1 (°C) TX2 (°C) D ( ⁇ ) a ( ⁇ ) Examle 4 475 560 340 2.86 7 485 610 300 2.85 Comp. Example 1 493 523 - -
  • the Table 2 data show that the ⁇ T value for the Examples 4 and 7 of the present invention are significantly larger than that of the Comparative Example 2. From the data shown in Table 2 above, it has been confirmed that the alloys of the present invention had crystalline particles of bcc solid solution, having a particle size of approximately 300 ⁇ and consisting mainly of iron, as formed by crystallization to be conducted by heat-treatment.
  • the first crystallization temperature TX1 is a temperature at which the Fe-base soft magnetic alloy samples may be produced by the use of a conventional heat-treatment device. Regarding the relationship between the first crystallization temperature TX1 and the second crystallization temperature TX2 of these samples, the difference between the two temperatures TX1 and TX2 was 95°C in the sample of Example 4 and was 125°C in the sample of Example 7, and in the comparative Example 2 was 30°C. From the data, it is understood that formation of crystals interfering with the soft magnetic property of the alloys may well be retarded by selection of the adequate heat-treatment temperature.
  • Example 9 Fe66Si14Al8Nb3B9, which has especially excellent characteristics of high permeability, low iron loss and low magnetostriction, was investigated and examined in more detail, and the results of the examination are mentioned below.
  • the alloy was formed into a ribbon sample having a width of 2.8 mm and a thickness of 17 ⁇ m by a single roll method.
  • X-ray diffraction image of the ribbon sample was obtained, immediately after quenched or after heat-treated in a nitrogen gas atmosphere at 580°C for one hour.
  • Fig. 4 shows the X-ray diffraction curves obtained, in which (a) indicates the quenched sample and shows a halo pattern which is specific to an amorphous alloy, and (b) indicates the heat-treated sample and shows a diffraction peak of specific bcc crystals. Specifically, the pattern (b) gives a peak indicating regular lattice reflection of DO3 structure in the low angle region.
  • the ribbon sample of the alloy of Example 9 (Fe66Si14Al8Nb3B9) was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 2.8 mm, which was then heat-treated in a nitrogen atmosphere for one hour.
  • the heat-treatment temperature dependence of the magnetic flux density B10 (T) and the coercive force Hc (mOe) of the coiled magnetic core sample under an applied magnetic field of 100 e was examined, which is shown in Fig. 5.
  • the magnetic flux density B10 is approximately 0.7 T in the heat-treatment temperature range of from 550°C to 670°C.
  • the coercive force Hc it has the minimum value of 12 mOe at 580°C and increases with elevation of the heat-treatment temperature.
  • Fig. 6 and Fig. 7 each show the heat-treatment temperature dependence of the effective magnetic permeability ⁇ e of the coiled magnetic core sample at various frequency and that of the iron loss (100 KHz, 0.1T) of the same, respectively. From Fig. 6, it is noted that the effective magnetic permeability ⁇ e has the maximum value at 580°C in a low frequency region (10 KHz or less) and then gradually decreases with elevation of the heat-treatment temperature in the same region. On the other hand, it is further noted that in a high frequency region (100 KHz or more), the temperature of giving the maximum value of the effective magnetic permeability is shifted to a high temperature side with elevation of the frequency. From Fig. 7, it is noted that the iron loss is satisfactorily low or is almost 10 W/g or so in the heat-treatment temperature range of from 580°C to 670°C.
  • Fig. 8 shows the heat-treatment temperature dependence of the crystal particle size D110 ( ⁇ ) as derived from the half-value width of the (110) diffraction intensity peak of bcc crystal of the alloy by the use of a Sheller's formula and the heat-treatment temperature dependence of the lattice constant a ( ⁇ ) as obtained from the (110) diffraction peak of the bcc crystal of the same.
  • the crystal particle size is always almost 140 A or so, irrespective of elevation of the heat-treatment temperature.
  • the lattice constant gradually decreases with elevation of the heat-treatment temperature.
  • Fig. 9 shows the heat-treatment temperature dependence of the saturation magnetostriction constant ⁇ s (x 10 ⁇ 6) of the alloy of Example 9 as heat-treated in a nitrogen gas atmosphere for one hour.
  • the saturation magnetostriction gradually decreases with elevation of the heat-treatment temperature.
  • the alloy sample shows an almost zero magnetostriction in a heat-treatment temperature range of 600°C or higher.
  • a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 2.8 mm was made of the alloy of example 9 of the present invention, which was heat-treated at 580°C or 600°C.
  • Fig. 10 shows the frequency characteristic of the effective magnetic permeability ⁇ e of each of the two heat-treated coiled magnetic core samples. It also shows the frequency characteristic of the effective magnetic permeability of alloys of Comparative Example 1 and Comparative Example 2 and a typical Mn-Zn ferrite. From Fig. 10, it is noted that the alloy of the present invention has a larger magnetic permeability value than the conventional amorphous alloy (Comparative Example 1) and Mn-Zn ferrite.
  • the alloy of the present invention has a higher effective magnetic permeability in a high frequency region of 100 KHz or more. From the data, it is understood that the alloy of the present invention is a novel fine crystalline soft magnetic alloy having excellent magnetic characteristics in a high frequency region.
  • Fig. 11 and Fig. 12 each show the frequency dependence (characteristic) and the magnetic flux density dependence, respectively, of the iron loss (W/g) of the Example 9 (580°C) coiled magnetic core sample as above. These also show the frequency dependence and the magnetic flux density dependence, respectively, of the iron loss of alloys of Comparative Example 1 and Comparative Example 2 and a typical Mn-Zn ferrite. Regarding the frequency dependence of the iron loss of each sample which is shown in Fig. 11, it is noted that the alloy of the present invention has a smaller iron loss than conventional amorphous alloy, Mn-Zn ferrite and fine crystalline soft magnetic alloy in a frequency range of from 10 KHz to 700 KHz.
  • the alloy of Example 9 (580°C) has a smaller iron loss than conventional amorphous alloy, Mn-Zn ferrite and fine crystalline soft magnetic alloy in a magnetic flux density range of from 0.1 T to 0.5 T.
  • a amorphous ribbon having a width of about 1.3 mm and a thickness of about 18 ⁇ m was formed from a melt containing Fe, Si, Al, B and Nb in an argon gas atmosphere of one atmosphere pressure by a single roll method.
  • the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 1.3 mm.
  • the alloy of the example 10-25 including no Ni shows very low magnetostriction in the range of 7-10 atomic % of the Al content.
  • a amorphous ribbon having a width of about 2.8 mm and a thickness of about 18 ⁇ m was formed by the same process of example 10 and the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 2.8 mm.
  • the effective permeability ( ⁇ ) a frequency of 100 KHz, an exciting magnetic field of 5mOe
  • the iron loss a frequency of 100 KHz, a maximum magnetic flux density of 0.1T
  • the alloy including more than 9 atomic % of B shows a low iron loss and a high permeability.
  • a amorphous ribbon having a width of about 1.3 mm and a thickness of about 18 ⁇ m was formed from a melt containing Fe, Si, Al, B, and M' in an argon gas atmosphere of one atmosphere pressure by a single roll method.
  • the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 1.3 mm.
  • the coercive force Hc (mOe), the permeability ( ⁇ ) (a frequency of 100 KHz, an exciting magnetic field of 5mOe) and the iron loss (a frequency of 100 KHz, a maximum magnetic flux density of 0.1T)of each core were measured.
  • a amorphous ribbon having a width of about 1.3 mm and a thickness of about 18 ⁇ m was formed by the same process of example 10 and the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 1.3 mm.
  • the effective permeability ( ⁇ ) a frequency of 100 KHz, an exciting magnetic field of 5mOe
  • the iron loss a frequency of 100 KHz, a maximum magnetic flux density of 0.1T
  • a amorphous ribbon having a width of about 2.8 mm and a thickness of about 18 ⁇ m was formed by the same process of example 10 and the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 2.8 mm.
  • the effective permeability ( ⁇ ) a frequency of 100 KHz, an exciting magnetic field of 5mOe
  • the iron loss a frequency of 100 KHz, a maximum magnetic flux density of 0.1T
  • the alloy of these examples shows an excellent value of an iron loss as well as a permeability.
  • the alloy of the present invention showed a high permeability in the high frequency range of 100 kHz or more by heat-treating in the presence of a magnetic field. Particularly in the range of 200 kHz or more, the alloy of the present invention showed higher permeability than that ( ⁇ ) of the ribbon (a comparative example 2, a width of 5 mm and a thickness of 18 ⁇ m) of a soft magnetic alloy having a good frequency characteristic which was heat-treated in the presence of a magnetic field.
  • the iron loss of the alloy of the present invention was sharply reduced by heat-treating in the presence of a magnetic field.
  • the value of the iron loss is lower than that ( ⁇ ) of the ribbon (a comparative example 2, a width of 5 mm and a thickness of 18 ⁇ m) which was heat-treated in the presence of a magnetic field.
  • the alloy of the present invention showed excellent soft magnetic properties by heat-treatment in the presence of a magnetic field.
  • X-ray diffraction image of Example 69 which was heat- treated for one hour in a nitrogen atmosphere is shown in Fig. 17.
  • a amorphous ribbon (Fe-Co-Si-Al-Nb-B) having a width of about 2.8 mm and a thickness of about 18 ⁇ m was formed by the same process of example 10 and the ribbon of the alloy was formed into a coiled magnetic core having an inner diameter of 15 mm, an outer diameter of 19 mm and a height of 2.8 mm. After the coiled core was optimum heat-treated in the absence of a magnetic field, further heat-treated in the presence of a magnetic field.
  • the permeability ( ⁇ ) (a frequency of 100 KHz, an exciting magnetic field of 5mOe) and the iron loss (a frequency of 100 KHz, a maximum magnetic flux density of 0.1T) of both pre-heat-treated core and a heat-treated core in a magnetic field were measured.
  • the composition of the alloy and the results obtained are shown in Table 8 below.
  • the alloy including Co instead of Ni shows as low iron loss as that including Ni, whereas some examples having Co show a lower permeability than the latter.
  • the content of crystal is 60 % or more in the alloy of the all examples above.
  • the present invention provides a novel Fe-base soft magnetic alloy as prepared by adding Al to an Fe-Si-B alloy composition, and the alloy has excellent soft magnetic properties.
  • the Fe-base soft magnetic alloy of the present invention has a large temperature difference between the crystallization temperature of crystals of showing a good soft magnetic property and the crystallization temperature of crystals of interfering with a soft magnetic property, the range of the temperature of heat treatment is sufficiently wider than that of the conventional amorphous alloys.
  • the Fe-base soft magnetic alloy of the present invention shows a very low magnetostriction by adding Al thereto and at the same time substituting Ni (Co) for a part of Fe, whereby a magnetic core having a low iron loss can be obtained.
  • Nb or the like element may be added to an Fe-Si-Al-B alloy composition to give a novel Fe-base soft magnetic alloy having excellent soft magnetic properties, especially having an extremely low coercive force, low iron loss and low magnetostriction as well as a high permeability in a high frequency region.
  • the alloy of the present invention possesses excellent properties as above-mentioned, it is useful for such applications as (material for magnetic core of) a high-frequency transformer, a common-mode choke coil, a magnetic amplifier, an inductor for filters, a transformer for signals, a magnetic head and so on.

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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)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
EP91920808A 1990-11-30 1991-11-29 Weichmagnetlegierung auf eisen-basis Expired - Lifetime EP0513385B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP334452/90 1990-11-30
JP33445290 1990-11-30
PCT/JP1991/001677 WO1992009714A1 (en) 1990-11-30 1991-11-29 Iron-base soft magnetic alloy

Publications (3)

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EP0513385A1 true EP0513385A1 (de) 1992-11-19
EP0513385A4 EP0513385A4 (en) 1993-05-05
EP0513385B1 EP0513385B1 (de) 1997-02-12

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EP (1) EP0513385B1 (de)
KR (1) KR950014314B1 (de)
CA (1) CA2074805C (de)
DE (1) DE69124691T2 (de)
WO (1) WO1992009714A1 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0713925A1 (de) * 1994-11-22 1996-05-29 Kawasaki Steel Corporation Amorphe Legierung auf Eisenbasis und Verfahren zu deren Herstellung
EP0747498A1 (de) * 1995-06-02 1996-12-11 Research Development Corporation Of Japan Glasartige Eisenlegierungen, mit einer grossen supergekühlter Temperaturspanne
WO1997025727A1 (en) * 1996-01-11 1997-07-17 Alliedsignal Inc. Distributed gap electrical choke
EP0899353A2 (de) * 1997-08-28 1999-03-03 Alps Electric Co., Ltd. Sinter- oder Gussstuck aus einer glasartige Eisenlegierungen
EP1198605A2 (de) * 1999-05-25 2002-04-24 Bechtel BWXT Idaho, LLC Verfahren zur stahlherstellung
WO2003067756A2 (en) * 2002-02-08 2003-08-14 Metglas, Inc. Filter circuit having an fe-based core
US7785428B2 (en) 2000-11-09 2010-08-31 Battelle Energy Alliance, Llc Method of forming a hardened surface on a substrate
CN102982955A (zh) * 2012-03-05 2013-03-20 宁波市普盛磁电科技有限公司 一种铁硅软磁粉末及其制备方法
WO2013173916A1 (en) * 2012-05-25 2013-11-28 HYDRO-QUéBEC Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings
EP2762902A3 (de) * 2013-01-31 2017-12-20 Siemens Aktiengesellschaft Gegenseitiger Strominduktor und Strommessschaltung dafür

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117026103A (zh) * 2023-08-08 2023-11-10 中南大学 一种高强高电阻低电阻温度系数的多组元软磁合金及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405368A (en) * 1981-05-07 1983-09-20 Marko Materials, Inc. Iron-aluminum alloys containing boron which have been processed by rapid solidification process and method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56158833A (en) * 1980-05-12 1981-12-07 Matsushita Electric Ind Co Ltd Wear resistant alloy
JP2625485B2 (ja) * 1988-03-23 1997-07-02 日立金属株式会社 電磁シールド材料
JPH07103453B2 (ja) * 1989-03-09 1995-11-08 日立金属株式会社 恒透磁率性に優れた合金およびその製造方法
JPH02170950A (ja) * 1989-09-11 1990-07-02 Tdk Corp 非晶質磁性合金材料

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405368A (en) * 1981-05-07 1983-09-20 Marko Materials, Inc. Iron-aluminum alloys containing boron which have been processed by rapid solidification process and method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9209714A1 *

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0713925A1 (de) * 1994-11-22 1996-05-29 Kawasaki Steel Corporation Amorphe Legierung auf Eisenbasis und Verfahren zu deren Herstellung
EP0747498A1 (de) * 1995-06-02 1996-12-11 Research Development Corporation Of Japan Glasartige Eisenlegierungen, mit einer grossen supergekühlter Temperaturspanne
KR100452535B1 (ko) * 1996-01-11 2004-12-17 메트글라스, 인코포레이티드 분포갭전기초크
WO1997025727A1 (en) * 1996-01-11 1997-07-17 Alliedsignal Inc. Distributed gap electrical choke
CN1114217C (zh) * 1996-01-11 2003-07-09 联合讯号公司 具有分布气隙的扼流圈
EP0899353A2 (de) * 1997-08-28 1999-03-03 Alps Electric Co., Ltd. Sinter- oder Gussstuck aus einer glasartige Eisenlegierungen
EP0899353A3 (de) * 1997-08-28 1999-05-19 Alps Electric Co., Ltd. Sinter- oder Gussstuck aus einer glasartige Eisenlegierungen
EP1198605A2 (de) * 1999-05-25 2002-04-24 Bechtel BWXT Idaho, LLC Verfahren zur stahlherstellung
EP1198605A4 (de) * 1999-05-25 2002-11-06 Bechtel Bwxt Idaho Llc Verfahren zur stahlherstellung
US7785428B2 (en) 2000-11-09 2010-08-31 Battelle Energy Alliance, Llc Method of forming a hardened surface on a substrate
US8097095B2 (en) 2000-11-09 2012-01-17 Battelle Energy Alliance, Llc Hardfacing material
WO2003067756A3 (en) * 2002-02-08 2004-02-26 Honeywell Int Inc Filter circuit having an fe-based core
US7541909B2 (en) 2002-02-08 2009-06-02 Metglas, Inc. Filter circuit having an Fe-based core
WO2003067756A2 (en) * 2002-02-08 2003-08-14 Metglas, Inc. Filter circuit having an fe-based core
CN102982955A (zh) * 2012-03-05 2013-03-20 宁波市普盛磁电科技有限公司 一种铁硅软磁粉末及其制备方法
CN102982955B (zh) * 2012-03-05 2015-03-11 宁波市普盛磁电科技有限公司 一种铁硅软磁粉末及其制备方法
WO2013173916A1 (en) * 2012-05-25 2013-11-28 HYDRO-QUéBEC Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings
CN104471097A (zh) * 2012-05-25 2015-03-25 魁北克水电公司 Fe3AlTa(Ru)型合金和其作为用于氯酸钠的合成的电极材料或作为耐腐蚀涂层的用途
EP2762902A3 (de) * 2013-01-31 2017-12-20 Siemens Aktiengesellschaft Gegenseitiger Strominduktor und Strommessschaltung dafür

Also Published As

Publication number Publication date
KR950014314B1 (ko) 1995-11-24
KR920703866A (ko) 1992-12-18
EP0513385A4 (en) 1993-05-05
CA2074805C (en) 2001-04-10
EP0513385B1 (de) 1997-02-12
DE69124691D1 (de) 1997-03-27
DE69124691T2 (de) 1997-06-19
CA2074805A1 (en) 1992-05-31
WO1992009714A1 (en) 1992-06-11

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