EP0513385A1 - Iron-base soft magnetic alloy - Google Patents
Iron-base soft magnetic alloy Download PDFInfo
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
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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
- C22C38/18—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.
Abstract
Description
- 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. However, though 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 Å 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 Å 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.
- However, when Cu is added to the alloy, Cu tends to gather by itself to cause heterogeneity of the alloy. Thereby, there can be such drawback as difficulty of forming a thin film by a single roll method or sticking of Cu to the nozzle which brings on a change in the composition of the alloy.
- On the other hand, regarding Cu-free fine crystalline soft magnetic alloys, Fe-Ta-C alloys have been reported (Hasegawa, et al., Journal of Applied Magnetics Society of Japan, 14, 313, 1990). However, these alloys could not be said sufficient in view of the practicability (economical efficiency) thereof.
- 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.
- Intense reserches and studies of various Fe-base soft magnetic alloys in view of the above objects have revealed that addition of Al to an Fe-base Fe-Si-B soft magnetic alloy can provide an improved Fe-base Fe-Si-B-Al soft magnetic alloy having excellent soft magnetic characteristics, for example, having an extremely low saturation magnetostriction, and that addition of other particular metal(s), especially Nb, to such an Fe-base Fe-Si-B-Al soft magnetic alloy is effective for obtaining excellent soft magnetic properties of the resulting alloy. The present invention is based on these findings.
- Specifically, there is provided in accordance with the present invention an Fe-base soft magnetic alloy which has a composition represented by the formula:
(Fe1-xMx)100-a-b-c-dSiaAlbBcM'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. In particular, 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 of an iron solid solution having a bcc structure. M' is preferably Nb. - 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.
- In the Fe-base soft magnetic alloy of the present invention, Fe may be substituted by Co and/or Ni in the range of from 0 to 0.15 for the value x. Since Co and Ni have a negative interaction parameter relative to Fe, it is believed that they are substituted for Fe in the bcc structure latice by dissolving in the Fe-major bcc solid solution formed during the heat treatment of the alloy of the present invention. Accordingly, it is believed that a magnetostriction constant and a magnetocrystalline anisotropy constant of the bcc solid solution would be reduced. Since the alloy of the present invention where the Ni (and/or Co) content (x) is 0 ≦ x ≦ 0.02, particulary x = 0, i.e. including no Ni nor Co, has a high permeability, it is preferably applied to such a use that requires a high permeability, as (material for magnetic core of) a common mode choke coil, an inductor for filters, transformers for signals and so on.
- On the other hand, in case that 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. Further, a magnetocrystalline anisotropy is sufficiently induced in the alloy by heat treatment in a magnetic field. Accordingly, 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. In this case, 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 (ΔT) 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. 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 (ΔT) between TX₁ and TX₂.
- In the present invention, 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. In case that the Ni/Co content (x) is 0 ≦ x < 0.02, especially x = 0, 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 %. - Since Al, similar to Ni (Co), has a negative interaction parameter relative to Fe, it is believed that addition of Al results in it's dissolution in the Fe-major solid solution, that is, dissolution in the way to be substituted for the Fe atom in the α-Fe crystal structure and stabilization of the bcc crystal. Thereby an environment of easy self-crystallization in the alloy during heat-treatment yields. Accordingly, since crystal grains having a small magnetocrystalline anisotropy are selectively formed in the alloy by addition of Al thereto, as mentioned above, it is believed that the alloy would have an excellent soft magnetic properties because of such morphology.
- 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 %. Within the determined range of B, 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 %. In the range of the content of B being 9.5-15 atomic %, particularly 10-14 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. In order to improve the corrosion-resistance and the magnetic properties of the alloy of the present invention, other element(s) M' may be added to the alloy. As 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. As these elements M', preferred are Nb, Ta, W, Mn, Mo and V. Above all, Nb is most preferred. Addition of Nb results in an extreme improvement of the soft magnetic properties, especially the coercive force, permeability and core loss of the alloy. 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.
- Incidentally, 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. In the present invention, even if the crystalline particles occupy substantially 100 % of the structure, 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.
- It is preferred that the crystalline particles to be formed in the alloy of the present invention have a particle size of 1000 Å or less, preferably 500 Å or less, more preferably 50 to 300 Å. The particle size being 1000 Å 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. Apart from this, it may also be determined from the ratio of the X-ray diffraction intensity of the diffracted X-rays to be proportional to crystallization of the alloy to the X-ray diffraction intensity by the halo effect which is specific to the amorphous phase to be decreased with progress of crystallization of the alloy.
-
- In general, 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. For instance, 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.
- Generally, 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. Preferably, it is carried out in vacuum or in an inert gas atmosphere. 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.
- By the heat treatment of the amorphous alloy being carried out in the aforementioned range of temperature and within the aforementioned time range, 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.
- Examples of the present invention is described hereinafter.
- A quenched ribbon sample having a width of about 1.0-5 mm and a thickness of about 14-20 µm 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.
- Other samples were formed in the same manner as above, except that the composition of Fe, Si, Al, B and Nb was varied as shown in Table 1, and these were heat-treated at an optimum temperature (°C) for about one hour and then cooled in a nitrogen stream. The coercive force Hc (mOe) and the saturation magnetization Ms (emu/g) of the heat-treated samples were measured. In addition, the saturation magnetostriction constant λs (×10⁻⁶) of each sample was measured by a strain gage method. The composition of the alloy was determined by IPC analysis.
- 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 (µ) 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.
- As comparative samples, 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.
Table 1 Composition Hc mOe Ms emu/g λs ×10-6 Iron Loss W/kg µ Particle Size Å Example1 Fe₇₃Si₈Al₁₀B₉ 95 165 6.2 100 1000 - 2 Fe₇₁Si₁₀Al₁₀B₉ 85 136 5.6 80 1500 - 3 Fe₆₇Si₁₂Al₁₂B₉ 50 110 3.0 65 2000 - 4 Fe₆₉Si₁₄Al₈B₉ 38 110 2.0 40 4000 340 5 Fe₆₈Si₁₃Al₈B₉ 75 110 2.2 45 2800 - 6 Fe₆₇Si₁₆Al₈B₉ 95 99 1.5 70 1700 - 7 Fe₆₈Si₁₄Al₈B₉Nb₁ 10 96 1.2 25 5400 300 8 Fe₆₇Si₁₄Al₈B₉Nb₂ 15 92 1.0 18 7200 - 9 Fe₆₆Si₁₄Al₈B₉Nb₃ 15 88 0.6 10 20000 140 Comp. Example1 Fe₇₈Si₉B₁₃ 50 167 27 40 6000 - 2 Fe73. 5Si13. 5B₉Cu₁Nb₃ 15 140 2.3 15 17000 - - As is obvious from the results in Table 1 above, the sample of 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.
- The sample of 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.
- Of these samples, 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 (Å) a (Å) 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 ΔT 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 Å 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.
- The alloy of 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.
- Precisely, the alloy was formed into a ribbon sample having a width of 2.8 mm and a thickness of 17 µm 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. As is obvious from 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. Regarding 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 µe 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 µe 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.
- Regarding the alloy of Example 9 as heat-treated for one hour in a nitrogen gas atmosphere, Fig. 8 shows the heat-treatment temperature dependence of the crystal particle size D₁₁₀ (Å) 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 (Å) as obtained from the (110) diffraction peak of the bcc crystal of the same. As is obvious from Fig. 8, the crystal particle size is always almost 140 A or so, irrespective of elevation of the heat-treatment temperature. On the other hand, however, it is noted that 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 λs (x 10⁻⁶) of the alloy of Example 9 as heat-treated in a nitrogen gas atmosphere for one hour. As is obvious from Fig. 9, the saturation magnetostriction gradually decreases with elevation of the heat-treatment temperature. In particular, it is noted that 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 µe 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. In addition, in comparison with the fine crystalline soft magnetic alloy having a good frequency characteristic (Comparative Example 2), it is noted that 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. Regarding the magnetic flux density dependence of the iron loss of each sample which is shown in Fig. 12, it is noted that 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. These results show that the alloy of the present invention has an excellent magnetic properties compared to the conventional alloy.
- A amorphous ribbon having a width of about 1.3 mm and a thickness of about 18 µm 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. After the coiled core was optimum heat-treated in the absence of a magnetic field, the coercive force Hc (mOe), the saturation magnetostriction constant λs (×10⁻⁶), the effective permeability (µ) (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. The composition of the samples and the results obtained are shown in Table 3 below.
Table 3 Coercive force (mOe) Saturation Magneization (× 10⁻⁶) Permeability (100KHz,5mOe) Iron Loss(W/kg) (100KHz,0.1T) Particle Size (Å) Example10 46 1.8 4000 52 160 11 36 1.5 3400 50 155 12 26 0.6 5600 30 145 13 22 0.5 3100 50 135 14 46 1.0 5400 30 160 15 30 1.1 8300 17 150 16 28 0.5 8600 20 145 17 16 0.2 8000 22 130 18 25 0.5 8600 22 160 19 28 0.1 9100 20 140 20 40 ∼0 8000 17 155 21 28 0.3 4400 28 165 22 26 0.1 9400 16 150 23 40 -0.2 4300 30 155 24 28 0.4 4400 28 160 25 42 -0.8 2200 50 165 Example 10 Fe₆₉Si₁₂Al₇Nb₃B₉ Example 11 Fe₆₈Si₁₂Al₈Nb₃B₉ Example 12 Fe₆₇Si₁₂Al₉Nb₃B₉ Example 13 Fe₆₆Si₁₂Al₁₀Nb₃B₉ Example 14 Fe₆₈Si₁₃Al₇Nb₃B₉ Example 15 Fe₆₇Si₁₃Al₈Nb₃B₉ Example 16 Fe₆₆Si₁₃Al₉Nb₃B₉ Example 17 Fe₆₅Si₁₃Al₁₀Nb₃B₉ Example 18 Fe₆₇Si₁₄Al₇Nb₃B₉ Example 19 Fe₆₅Si₁₄Al₉Nb₃B₉ Example 20 Fe₆₄Si₁₄Al₁₀Nb₃B₉ Example 21 Fe₆₆Si₁₅Al₇Nb₃B₉ Example 22 Fe₆₅Si₁₅Al₈Nb₃B₉ Example 23 Fe₆₄Si₁₅Al₉Nb₃B₉ Example 24 Fe₆₅Si₁₆Al₇Nb₃B₉ Example 25 Fe₆₄Si₁₆Al₈Nb₃B₉ - As is obvious from the results in Table 3 above, 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 µm 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, the effective permeability (µ) (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. The composition of the samples and the results obtained are shown in Table 4 below.
Table 4 Composition (atom%) Permeability µ (100KHz,5mOe) Iron Loss(W/kg) (100KHz,0.1T) Example 26 Fe65. 5Si₁₄Al₈Nb₃B9. 5 14000 12 27 Fe₆₅Si₁₄Al₈Nb3. 5B9. 5 19000 9 28 Fe₆₅Si13. 9Al7. 8Nb3. 3B₁₀ 20000 10 29 Fe₆₄Si₁₄Al₈Nb₄B₁₀ 17000 10 30 Fe₆₄Si13. 5Al7. 5Nb₄B₁₁ 12000 12 31 Fe₆₅Si₁₄Al₈Nb₄B9. 5 16000 14 32 Fe₆₉Si₁₃Al₄Nb₄B₁₀ 7000 22 33 Fe₆₇Si₁₃Al₆Nb₄B₁₀ 12000 16 34 Fe63. 7Si₁₃Al₁₀Nb3. 3B₁₀ 14000 9 35 Fe₆₁Si₁₃Al₁₂Nb₄B₁₀ 10000 16 36 Fe63. 5Si₁₃Al7. 5Nb₄B₁₂ 9000 18 37 Fe₆₀Si12. 8Al7. 2Nb₆B₁₄ 7800 20 38 Fe₆₁Si₁₆Al₉Nb₄B₁₀ 5000 34 39 Fe₅₈Si₁₈Al₁₀Nb₄B₁₀ 4200 46 - As is obvious from the results in Table 4 above, 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 µm 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. After the coiled core was optimum heat-treated in the absence of a magnetic field, the coercive force Hc (mOe), the permeability (µ) (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. The composition of the samples and the results obtained are shown in Table 5 below.
Table 5 Coercive Force (mOe) Permeability (100KHz,5mOe) Iron Loss(W/kg) (100KHz,0.1T) Example 40 26 13800 15 41 56 13200 12 42 18 4000 40 43 22 5000 30 44 28 6000 24 45 20 14000 15 46 50 4200 40 47 22 11000 18 48 24 11000 15 49 28 5000 26 50 20 12000 18 51 28 8000 24 52 28 8200 22 53 32 11000 18 54 26 9000 20 55 26 8000 28 56 30 8000 32 57 28 7000 30 58 46 6000 26 59 42 5200 42 Example 40 Fe₆₆S₁₄Al₈Mo₃B₉ 41 Fe₆₆Si₁₄Al₈Ta₃B₉ 42 Fe₆₆Si₁₄Al₈Cr₃B₉ 43 Fe₆₆Si₁₄Al₈V₃B₉ 44 Fe₆₆Si₁₄Al₈Ti₃B₉ 45 Fe₆₆Si₁₄Al₈W₃B₉ 46 Fe₆₆Si₁₄Al₈Mn₃B₉ 47 Fe₆₆Si₁₄Al₈Hf₃B₉ 48 Fe₆₆Si₁₄Al₈Zr₃B₉ 49 Fe₆₆Si₁₄Al₈Y₃B₉ 50 Fe₆₄Si₁₄Al₈Nb₂Mo₂B₁₀ 51 Fe₆₂Si₁₃Al₈Nb₃Ta₂B₁₂ 52 Fe₆₃Si₁₃Al₈Nb₃Zr₁B₁₂ 53 Fe₆₅Si₁₃Al₈Mo₂W₂B₁₀ 54 Fe₆₃Si₁₃Al₇Nb₄Pd₃B₁₀ 55 Fe₆₃Si₁₃Al₆Nb₄Ru₄B₁₀ 56 Fe₆₆Si₁₄Al₄Ga₄Nb₄B₁₀ 57 Fe₆₆Si₁₄Al₆Ge₃Nb₄B₁₀ 58 Fe₆₁Si₁₄Al₈Zr₄B₉C₄ 59 Fe₆₃Si₁₄Al₆Zr₄B₁₀P₃ - As is obvious from the results in Table 5 above, both amorphous alloys including an other element than Nb as M'(examples 40-49, 53, 53 and 59) and alloys including the element together with Nb show excellent magnetic characteristics.
- A amorphous ribbon having a width of about 1.3 mm and a thickness of about 18 µm 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. After the coiled core was optimum heat-treated in the absence of a magnetic field, the effective permeability (µ) (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. The composition of the samples and the results obtained are shown in Table 6 below.
Table 6 Composition (atom%) Permeability µ (100KHz) Iron Loss(W/kg) (100KHz,0.1T) Example 60 Fe₇₅Si₈Al₅Nb₃B₉ 3400 40 61 Fe₇₄Si₉Al₅Nb₃B₉ 4600 37 62 Fe₇₄Si₈Al₆Nb₃B₉ 2600 46 63 Fe₇₃Si₁₀Al₅Nb₃B₉ 2000 58 64 Fe₇₁Si₉Al₆Nb₄B₁₀ 5100 32 65 Fe69. 7Si8. 6Al5. 7Nb₄B₁₂ 5000 36 66 Fe₆₆Si₈Al₅Nb₅B₁₆ 1000 100 - A amorphous ribbon having a width of about 2.8 mm and a thickness of about 18 µm 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, the effective permeability (µ) (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. The composition of the samples and the results obtained are shown in Table 7 below.
Table 7 Before Heat-treatment After Heat-treatme Particle Size Å In the Presence of a Magnetic Field Permeability (100KHz,5mOe) Iron Loss (W/Kg) (100KHz,0.1T) Permeability (100KHz,5mOe) Iron Loss (W/Kg) (100KHz,0.1T) Example67 9000 20 10000 14 140 68 13000 13 14000 9 140 69 13000 12 10000 9 140 70 13000 12 9000 8 140 71 6000 30 5000 18 150 72 8000 25 9000 15 - 73 10000 20 9000 15 150 74 11000 18 9400 12 150 75 10000 16 9000 12 150 76 9800 20 9600 16 - 77 9600 18 8800 12 - 78 9400 16 9000 12 - 79 8600 18 8600 14 - 80 8400 18 8600 14 - 81 8600 20 8800 16 - Example 67 Fe₆₆Ni1. 6Si₁₄Al6. 4Nb₃B₉ 68 Fe₆₆Ni3. 2Si₁₄Al4. 8Nb₃B₉ 69 Fe₆₆Ni₄Si₁₄Al₄Nb₃B₉ 70 Fe₆₆Ni4. 8Si₁₄Al3. 2Nb₃B₉ 71 Fe₆₆Ni5. 5Si₁₄Al2. 5Nb₃B₉ 72 Fe69. 4Ni2. 4Si9. 6Al6. 6Nb₃B₉ 73 Fe₆₆Ni2. 8Si11. 2Al₈Nb₃B₉ 74 Fe₆₅Ni₄Si₁₄Al₄Nb3. 5B9. 5 75 Fe₆₅Ni4. 8Si₁₄Al3. 2Nb3. 5B9. 5 76 Fe₆₄Ni₄Si₁₄Al₄Nb₄B₁₀ 77 Fe64. 5Ni4. 8Si13. 5Al3. 2Nb₄B₁₀ 78 Fe₆₄Ni₄Si₁₃Al₄Nb₄B₁₁ 79 Fe₆₃Ni4. 8Si₁₃Al3. 2Nb₄B₁₂ 80 Fe₆₂Ni4. 5Si₁₃Al₄Nb4. 5B₁₂ 81 Fe₅₉Ni₄Si₁₃Al₄Nb₆B₁₄ - As is obvious from the results in Table 7 above, the alloy of these examples shows an excellent value of an iron loss as well as a permeability.
- Further, the frequency dependence of the effect permeability (µ) and the iron loss of the Example 69 ( ⃝) which was heat-treated in the absence of a magnetic field was measured. At the same time, the frequency dependence of the effect permeability (µ) and the iron loss of the Example 69 (●) which was heat-treated in the presence of a magnetic field was measured. The results obtained are shown in Figs. 13 and 14. B-H loops in the exciting magnetic field (Hm) of 100 e, 10 e and 0.10 e are also illustrated in Figs. 15 and 16.
- As is obvious from Fig. 13, 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 (Δ) of the ribbon (a comparative example 2, a width of 5 mm and a thickness of 18 µm) of a soft magnetic alloy having a good frequency characteristic which was heat-treated in the presence of a magnetic field.
- As is obvious from Fig. 14, 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 (Δ) of the ribbon (a comparative example 2, a width of 5 mm and a thickness of 18 µm) which was heat-treated in the presence of a magnetic field.
- Further, as is obvious from comparison of B-H loop of the pre-heat-treated alloy and that of the heat-treated alloy, 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 µm 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 (µ) (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.
Table 8 Before Heat-treatment After Heat-treatment In the Presence of a Magnetic Field Iron Loss (W/Kg) (100KHz,0.1T) Permeability (100KHz,5mOe) Iron Loss (W/Kg) (100KHz,0.1T) Permeability (100KHz,5mOe) Example 82 18 11000 13 12000 83 16 7100 14 7200 84 28 3900 24 3800 85 57 2800 48 2800 86 30 5100 25 6000 Example 82 Fe₆₆Co1. 6Si₁₄Al6. 4Nb₃B₉ 83 Fe₆₆Co3. 2Si₁₄Al4. 8Nb₃B₉ 84 Fe₆₆Co₄Si₁₄Al₄Nb₃B₉ 85 Fe₆₆Co2. 8Si11. 2Al₈Nb₃B₉ 86 Fe₆₆Co5. 6Si8. 4Al₈Nb₃B₉ - As is obvious from the results in Table 8 above, 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 (fine crystalline particles) is 60 % or more in the alloy of the all examples above.
- As is obvious from the results in the above-mentioned examples, 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. In addition, since 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.
- Furthermore, in accordance with the present invention, 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.
- Since 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.
Claims (17)
- An Fe-base soft magnetic alloy having a composition as represented by the general formula:
(Fe1-xMx)100-a-b-c-dSiaAlbBcM'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. - The Fe-base soft magnetic alloy as claimed in claim 1, in which at least 30 % of the alloy structure is occupied by a crystalline phase with the balance being an amorphous phase.
- The Fe-base soft magnetic alloy as claimed in claim 2, in which the crystalline phase is bcc solid solution consisting mainly of iron.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which M' is Nb.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content(x) of M is x=0.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (x) of M is 0.02 ≦ x ≦ 0.15.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (x) of M is 0.03 ≦ x ≦ 0.1.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which M is Ni.
- The Fe-base soft magnetic alloy as claimed in claim 6, in which M is Ni.
- The Fe-base soft magnetic alloy as claimed in claim 7, in which M is Ni.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (b) of Al is 2.5 ≦ b ≦ 15.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (b) of Al is 3 ≦ b ≦ 12.
- The Fe-base soft magnetic alloy as claimed in claim 8, in which the content (b) of Al is 3 ≦ b ≦ 10.
- The Fe-base soft magnetic alloy as claimed in claim 5, in which the content (b) of Al is 7 ≦ b ≦ 12.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (c) of B is 6 ≦ c ≦ 15.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (c) of B is 9.5 ≦ c ≦ 15.
- The Fe-base soft magnetic alloy as claimed in claim 1, in which the content (c) of B is 10 ≦ c ≦ 14.
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JP33445290 | 1990-11-30 | ||
JP334452/90 | 1990-11-30 | ||
PCT/JP1991/001677 WO1992009714A1 (en) | 1990-11-30 | 1991-11-29 | Iron-base soft magnetic alloy |
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EP0513385A1 true EP0513385A1 (en) | 1992-11-19 |
EP0513385A4 EP0513385A4 (en) | 1993-05-05 |
EP0513385B1 EP0513385B1 (en) | 1997-02-12 |
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EP (1) | EP0513385B1 (en) |
KR (1) | KR950014314B1 (en) |
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WO (1) | WO1992009714A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0713925A1 (en) * | 1994-11-22 | 1996-05-29 | Kawasaki Steel Corporation | Amorphous iron based alloy and method of manufacture |
EP0747498A1 (en) * | 1995-06-02 | 1996-12-11 | Research Development Corporation Of Japan | Ferrous glassy alloy with a large supercooled temperature interval |
WO1997025727A1 (en) * | 1996-01-11 | 1997-07-17 | Alliedsignal Inc. | Distributed gap electrical choke |
EP0899353A2 (en) * | 1997-08-28 | 1999-03-03 | Alps Electric Co., Ltd. | Sinter and casting comprising Fe-based high-hardness glassy alloy |
EP1198605A2 (en) * | 1999-05-25 | 2002-04-24 | Bechtel BWXT Idaho, LLC | Methods of forming steel |
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 (en) * | 2012-03-05 | 2013-03-20 | 宁波市普盛磁电科技有限公司 | Iron-silicon soft magnetic alloy power and manufacturing method thereof |
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 (en) * | 2013-01-31 | 2017-12-20 | Siemens Aktiengesellschaft | Current mutual inductor and current detection circuit of same |
Citations (1)
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)
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 (en) * | 1988-03-23 | 1997-07-02 | 日立金属株式会社 | Electromagnetic shielding material |
JPH07103453B2 (en) * | 1989-03-09 | 1995-11-08 | 日立金属株式会社 | Alloy with excellent permeability and method for producing the same |
JPH02170950A (en) * | 1989-09-11 | 1990-07-02 | Tdk Corp | Amorphous magnetic alloy material |
-
1991
- 1991-11-29 EP EP91920808A patent/EP0513385B1/en not_active Expired - Lifetime
- 1991-11-29 WO PCT/JP1991/001677 patent/WO1992009714A1/en active IP Right Grant
- 1991-11-29 KR KR1019920701773A patent/KR950014314B1/en not_active IP Right Cessation
- 1991-11-29 CA CA002074805A patent/CA2074805C/en not_active Expired - Fee Related
- 1991-11-29 DE DE69124691T patent/DE69124691T2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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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)
Title |
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See also references of WO9209714A1 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0713925A1 (en) * | 1994-11-22 | 1996-05-29 | Kawasaki Steel Corporation | Amorphous iron based alloy and method of manufacture |
EP0747498A1 (en) * | 1995-06-02 | 1996-12-11 | Research Development Corporation Of Japan | Ferrous glassy alloy with a large supercooled temperature interval |
KR100452535B1 (en) * | 1996-01-11 | 2004-12-17 | 메트글라스, 인코포레이티드 | Distributed Gap Electrical Choke |
WO1997025727A1 (en) * | 1996-01-11 | 1997-07-17 | Alliedsignal Inc. | Distributed gap electrical choke |
CN1114217C (en) * | 1996-01-11 | 2003-07-09 | 联合讯号公司 | Distributed gap electrical choke |
EP0899353A2 (en) * | 1997-08-28 | 1999-03-03 | Alps Electric Co., Ltd. | Sinter and casting comprising Fe-based high-hardness glassy alloy |
EP0899353A3 (en) * | 1997-08-28 | 1999-05-19 | Alps Electric Co., Ltd. | Sinter and casting comprising Fe-based high-hardness glassy alloy |
EP1198605A2 (en) * | 1999-05-25 | 2002-04-24 | Bechtel BWXT Idaho, LLC | Methods of forming steel |
EP1198605A4 (en) * | 1999-05-25 | 2002-11-06 | Bechtel Bwxt Idaho Llc | Methods of forming steel |
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 (en) * | 2012-03-05 | 2013-03-20 | 宁波市普盛磁电科技有限公司 | Iron-silicon soft magnetic alloy power and manufacturing method thereof |
CN102982955B (en) * | 2012-03-05 | 2015-03-11 | 宁波市普盛磁电科技有限公司 | Iron-silicon soft magnetic alloy power and manufacturing method thereof |
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 (en) * | 2012-05-25 | 2015-03-25 | 魁北克水电公司 | Alloys of the type fe3alta(ru) and use thereof as electrode material for the synthesis of sodium chlorate or as corrosion resistant coatings |
EP2762902A3 (en) * | 2013-01-31 | 2017-12-20 | Siemens Aktiengesellschaft | Current mutual inductor and current detection circuit of same |
Also Published As
Publication number | Publication date |
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CA2074805A1 (en) | 1992-05-31 |
DE69124691T2 (en) | 1997-06-19 |
KR920703866A (en) | 1992-12-18 |
CA2074805C (en) | 2001-04-10 |
EP0513385B1 (en) | 1997-02-12 |
WO1992009714A1 (en) | 1992-06-11 |
KR950014314B1 (en) | 1995-11-24 |
DE69124691D1 (en) | 1997-03-27 |
EP0513385A4 (en) | 1993-05-05 |
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