WO2002077300A1

WO2002077300A1 - Production of soft magnetic formed body of high permeability and high saturation magnetic flux density

Info

Publication number: WO2002077300A1
Application number: PCT/JP2002/002788
Authority: WO
Inventors: Akihiro Makino
Original assignee: Ohnishi, Kazumasa
Priority date: 2001-03-21
Filing date: 2002-03-22
Publication date: 2002-10-03
Also published as: JP2006040906A

Abstract

A soft magnetic formed body is produced by a method comprising a step of producing a thin sheet bendable by 180 °C and having a multiphase structure where an α-Fe crystal phase having an average particle size of 1-43 nm is dispersed in an amorphous phase by rapidly solidifying a molten Fe-based alloy composition containing Fe the content of which is 80-90 atom% and a step of heating the thin sheet to a temperature higher than the crystallization temperature of the α-Fe crystal phase. The thus produced soft magnetic formed body has a permeability of 1000 or more at a frequency of 1 kHz, a saturation magnetic flux density of 1.5 T or more, and a core loss of 0.15 W/kg or less at a frequency of 50 Hz.

Description

Manufacturing of soft magnetic compacts with high magnetic permeability and high saturation magnetic flux density

[Technical field]

The present invention relates to a soft magnetic alloy that is widely used as a magnetic material for electric appliances such as various transformers, choke coils, and motors. The present invention relates to a soft magnetic compact having an alloy composition. [Background technology]

The characteristics generally required for soft magnetic alloys used in various transformers, choke coils, motors, etc. are that, in addition to low coercive force, high saturation magnetic flux density, high magnetic permeability, and processing That is good. From the viewpoint of industrial materials, it is essential that they be inexpensive and easy to manufacture.

Conventionally, crystalline alloys such as Sendust, Parmalloy, and copper silicon have been used for the above applications, but recently Fe-based and Co-based amorphous alloys have become amorphous. Nanocrystalline alloys produced by heat treating alloys are also being used.

In the case of small transformers and choke coils, further miniaturization is required in accordance with the miniaturization of electronic devices, and magnetic materials with higher performance are desired.

Furthermore, from the viewpoint of recent global warming countermeasures, electric power used at commercial frequencies, electrical equipment such as pole transformers, and the like, require a saturation magnetic flux density of 1.4 T or more and low core loss. However, although Sendust has excellent soft magnetic properties, it has a drawback of low saturation magnetic flux density of about 1.1 mm.Permalloy also has a composition with excellent soft magnetic properties, and has a saturation magnetic flux density of about 0.8 T. Silicon copper has a disadvantage that silicon copper has a high saturation magnetic flux density but is inferior in soft magnetic properties.

On the other hand, among amorphous alloys, the Co-based alloy has excellent soft magnetic properties, but the saturation magnetic flux density is as low as about 1.0 T, which is insufficient. In addition, the Fe-based amorphous alloys known so far have a high saturation magnetic flux density depending on the composition, and have a magnetic flux density of 1.5 T or more. However, those with alloy compositions showing high saturation magnetic flux density have insufficient magnetic properties.

By the way, looking at the relationship between the magnetic properties of these conventional magnetic materials and the magnetic properties required of practical magnetic devices, transformers that are used at several 10 kHz from the commercial frequency require less power to handle. In many cases, the saturation magnetic flux density of the core material used for them is desired to be as large as possible.

For example, in recent years, pole transformers and the like have been required to have a saturation magnetic flux density of 1.4 T or more, and in fact, silicon copper having a saturation magnetic flux density of 1.5 T or more, or 1. Fe-based amorphous alloys with a saturation magnetic flux density of 3 T or more are used despite their unsatisfactory magnetic permeability.

In such a case, if the magnetic material constituting the core material has a high magnetic permeability, the efficiency as a transformer is improved. In particular, if a magnetic permeability of 1000 or more is obtained, the merits become remarkable. Actually, there is no practical magnetic material with a magnetic permeability of 5 T or more.

As is well known, ordinary soft magnetic materials are used in the frequency band of several Hz to several hundred Hz, but in this range, high saturation magnetic flux density and high magnetic permeability can be realized at the same time. It is well known that if a soft magnetic material can be obtained, magnetic components such as transformers can be reduced in size and reduced in energy loss. That is, the higher the saturation magnetic flux density of the soft magnetic material, the higher the magnetic flux, and consequently the volume of the magnetic component can be reduced. Furthermore, since most of the energy loss of magnetic components is released to the outside as heat, it is generally necessary to devise a space between other devices and components. This was a major obstacle to miniaturization. Therefore, if the size of the magnetic component is reduced, the above-described problem can be solved. As a result, the size of the entire magnetic device can be reduced.

However, as described above, conventional soft magnetic materials having a high saturation magnetic flux density tend to have a low magnetic permeability.Specifically, saturated soft magnetic materials are saturated in practical Fe-based amorphous alloys. If the magnetic flux density is 1.3 to 1.5 T, the magnetic permeability tends to be about 900 by dividing the magnetic permeability of 10000, and the magnetic permeability of a practical Co-based amorphous alloy is 10 0 If it is more than 0000, it tends to be less than 1.0T. In recent years, nanocrystalline alloys with excellent magnetic properties have been found by heating and crystallizing the FΘ-based amorphous phase. Obtaining a single phase was considered essential. For this reason, the alloy composition must contain a large amount of amorphous forming elements, which inevitably limits the Fe concentration, and it has been said that the saturation magnetic flux density of the obtained magnetic material is limited. That is, when the alloy composition contains Fe exceeding the limit of about 80 atomic%, the crystalline phase is mixed with the amorphous phase obtained by the liquid quenching, the material becomes brittle, and the workability is reduced. It has been pointed out that there is a problem that the magnetic properties are significantly worsened and the soft magnetic properties are also significantly degraded.

On the other hand, Fe-based soft magnetic alloys that use a large amount of Zr as an amorphous forming element require an oxygen gas concentration in the atmosphere during the heating process in order to prevent oxidation of Zr during the heating process during production. Therefore, it is necessary to control the temperature at a low level, so that a manufacturing operation using a device equipped with a vacuum device is required, and there is a problem that industrial application is disadvantageous.

Therefore, a practical soft magnetic material which has high saturation magnetic flux density and high magnetic permeability as described above, has thermal stability, and is inexpensive and easy to manufacture is desired. Therefore, an object of the present invention is to provide a soft magnetic compact made of an Fe-based alloy that has both a high saturation magnetic flux density of 1.5 T or more and a high magnetic permeability of 1000 or more and is easily industrially manufactured. Is to provide.

[Disclosure of the Invention]

The present inventor has sought to solidify a Fe-based alloy composition in a molten state by rapid cooling and solidification to produce a bendable amorphous ribbon, and then heat the ribbon to form a soft magnetic molded body. Even if the Fe content of the Fe-based alloy composition used in the production method is as high as 80 to 90 atomic%, the dispersion state of the fine crystalline Fe phase Then, the ribbon is heated at a temperature equal to or higher than the crystallization temperature of the _F e crystal phase, so that the magnetic permeability at a frequency of 1 kHz is 100,000 or higher, and the saturation magnetic flux is The present inventors have found that a soft magnetic molded body having a density of 1.5 T or more and a magnetic core loss at a frequency of 50 Hz of 0.15 W / kg or less can be easily obtained, and arrived at the present invention.

Therefore, the present invention relates to a Fe group having a Fe content of 80 to 90 atomic% in a molten state. The alloy composition is rapidly solidified to have a mixed phase structure in which an amorphous phase is formed of a dispersed Fe-crystalline phase having an average particle size of 1 to 42 nm, and a 180 ° fold. Producing a bendable ribbon, and heating the ribbon to a temperature above the crystallization temperature of the —: Fe crystalline phase, at a frequency of 1 kHz. The method is for manufacturing a soft magnetic molded body having a magnetic permeability of 10,000 or more, a saturation magnetic flux density of 1.5 T or more, and a core loss at a frequency of 50 Hz of 0.15 W dakg or less.

The present invention also includes an Fe-based alloy composition having an Fe content of 80 to 90 atomic%, a magnetic permeability at 1 kHz frequency of 10,000 or more, a saturation magnetic flux density of 1.5 T or more, and a frequency of 50 Hz ( Core loss of 0.15 W / kg or less.

The present invention also resides in a wound core formed by winding the soft magnetic molded body as a thin strip having a thickness of 5 to 100 m and winding the thin strip.

Furthermore, the present invention relates to a method for producing a molten metal having a Fe content ratio of 80 to 90 atomic%. The e-base alloy composition is rapidly solidified to have a mixed phase structure in which an o: _Fe crystal phase having an average particle size in the range of 1 to 42 nm is formed in a dispersed state in an amorphous phase, and 180 ° There is also a method for producing a ribbon having a thickness of 5 to 100 / m of a Fe-based alloy composition that can be bent.

The present invention also provides an Fe-based alloy composition having an Fe content of 80 to 90 atomic%, and a crystalline phase of Fe Fe having an average particle size in the range of 1 to 42 nm is dispersed in an amorphous phase. A Fe-based alloy composition having a formed multiphase structure and capable of bending at 180 ° is also present in a ribbon having a thickness of 5 to 100 μm.

Preferred embodiments of the soft magnetic molded article and the ribbon according to the present invention, and the methods for producing them are as follows.

(1) The average grain size of the Hi-Fe crystal phase in the ribbon is in the range of 1 to 40 nm (particularly 1 to 35 nm).

(2) The abundance ratio of the α-Fe fine crystal phase in the ribbon is 5 to 30% by volume.

(3) Manufacture the ribbon to have a thickness of 5 to 100 m.

(4) Before heating the ribbon, perform one or more of winding, punching, etching, surface polishing, and slitting. (5) one or more elements selected from the group consisting of 1 to 10 atomic% of 1), W, Ta, ZR, Hf, Ti and Mo, wherein the Fe-based alloy composition is 0.5 to 25; Atomic% of B, and 0.01 to 5 atomic% of P, Cu, V, Cr, Mn, Al, platinum group elements, Sc, Y, rare earth elements, Au, Zn, Sn, Re, Ag, Including one or more elements selected from the group consisting of C, Ge, Sb, In, As, Be, and Si.

(6) one or more elements selected from the group consisting of 2 to 10 atomic% of Nb and Hf, 0.5 to 25 atomic% of 5, and 0.01 to 5 atomic% of the Fe-based alloy composition; % ^: Includes one or more elements selected from the group consisting of 0, P, Cu, and C. '

(7) The Fe content of the Fe-based alloy composition is at least 82 atomic%.

(8) The magnetic permeability at a frequency of 1 kHz of the soft magnetic molded body is 15,000 or more. (9) The magnetic core loss at a frequency of 50 Hz of the soft magnetic molded body is 0.14 WZkg or less.

[Brief description of drawings]

FIG. 1 is an example of an X-ray diffraction pattern of the Fe alloy composition according to the material of the present invention in a quenched state.

FIG. 2 shows an example of the change in the magnetic permeability after the heat treatment of the Fe alloy composition containing no P with respect to the B content.

FIG. 3 is an example of the change in the magnetic permeability after the heat treatment of the Fe alloy composition containing 1 atomic% of P with respect to the B + P content.

FIG. 4 is an example of a change in the X-ray diffraction pattern of the Fe alloy composition according to the present invention with respect to the Cu content.

FIG. 5 is an example of a change in the magnetic permeability of the Fe alloy composition according to the present invention after the heat treatment with respect to the Cu content.

FIG. 6 is an example of a change in the X-ray diffraction pattern of the Fe alloy composition according to the present invention with respect to the P content.

FIG. 5 shows the magnetic permeability after heat treatment of the Fe alloy composition according to the present invention with respect to the P content. This is an example of a change. [Detailed description of the invention]

The soft magnetic molded article of the present invention has a high toughness such that the molten metal of the Fe-based alloy composition is rapidly solidified in a thin strip shape, and the thin strip is not damaged by bending at 180 °. A step of forming a mixed phase structure of a fine single Fe crystal phase having an average crystal grain size of 1 to 42 nm and an amorphous phase, and, if necessary, the strip obtained in this step. After performing one or more processing operations such as winding, punching, etching, surface polishing, and slitting, a heat treatment is performed at a temperature higher than the crystallization temperature of the Fe-based alloy composition.

If the average crystal grain size of the α-Fe crystal phase in the ribbon formed by rapid solidification of the molten metal exceeds 5 O nm, the toughness of the ribbon decreases, making it difficult to process subsequent windings. Become

It is essential that the Fe-based alloy composition, which is a material used in the present invention, contains an amorphous forming element. B. (boron) is a typical amorphous-forming element, and has the effect of increasing the ability to form an amorphous phase of the material of the present invention, and also suppresses the formation of a compound phase that adversely affects magnetic properties in the heat treatment step. It is thought to be effective. However, when a large amount of B is contained, the saturation magnetic flux density decreases due to a decrease in the Fe concentration of the material, or a tendency to form a boride of Fe after heat treatment appears, and the magnetic property of the soft magnetic compact formed is increased. It is not preferable because it causes deterioration of characteristics. Therefore, the preferable content of B in the material of the present invention is 0.5 to 25 atomic%, more preferably 0.5 to 15 atomic%. Further, in order to obtain a material which is easy to produce and has better magnetic properties, the B content is preferably 5 to 12 atomic%.

The inclusion of Cu (copper) is thought to have the effect of reducing the grain size of the Fe crystalline phase formed during quenching, and has the effect of making it easier to obtain a material that exhibits high toughness in the quenched state. . However, when the content of Cu increases, Cu crystals are generated in the amorphous phase in a quenched state, and the toughness of the material decreases. Therefore, the preferable content of Cu in the material of the present invention is 1.5 atomic% or less. Further, in order to obtain a material exhibiting more excellent magnetic properties, the content of Cu is preferably 1 atomic% or less, more preferably 0.5 atomic% or less. It is.

P, like B, is considered to have the effect of further increasing the ability of the material of the present invention to form an amorphous phase and the effect of suppressing the formation of a compound phase that adversely affects magnetic properties in the heat treatment step. It is considered that the simultaneous formation of B and P further enhances the ability to form an amorphous phase, and makes it easier to obtain a mixed phase structure of an amorphous phase with a higher Fe concentration and a single Fe crystal phase. Is considered more preferable. However, including a large amount of P is not preferable because it lowers the Fe concentration and the saturation magnetic flux density. Therefore, the preferable content of P in the material of the present invention is 5 atomic% or less. In order to obtain a material having better magnetic properties, the P content is preferably 1.5 atomic% or less.

When the present invention is used as a magnetic core material for magnetic components such as various transformers, choke coils, and motors, high permeability, high performance, small size, and high efficiency are required for these magnetic components. It is necessary to have various characteristics such as high saturation magnetic flux density, and low core loss. Specifically, it is preferable that the magnetic permeability at a frequency of 1 kHz is 10,000 or more, the saturation magnetic flux density is 1.5 T or more, and the core loss at a frequency of 50 Hz is 0.15 W / kg or less.

In order to realize the above magnetic properties, a composition expressed by the following formula (1) containing an element such as Nb as an essential element, and further containing other elements such as B capable of forming an amorphous phase, is required. Preferably, it is an Fe-based alloy.

(Fei-aMaixoO-bcdefs-hM ⁵ _b B. P _d C u _e M " _f M,: _h —- (1)

[Where M is one or both of Co and Ni, and M 'is one or more elements selected from the group consisting of Nb, W, Ta, Zr, Hf, Ti and Mo] And M "is one or more elements selected from the group consisting of V, Cr, Mn, A1, platinum group elements, Sc, Y, rare earth elements, Au, Zn, Sn, Re, and Ag. Is a kind or two or more kinds of elements selected from the group consisting of C, Ge ₃ Sb, In, As, Be, and X is one or both of S i and A 1; , B, c, d, e, f, g, h are 0≤a≤0.5, 1≤b≤10. 5≤c≤25, 0≤d≤5 0≤ e≤1.5, 0≤f≤2, 0≤g≤3, 0≤h≤6 (However, the total amount of Fe and M is 80 To 90 atomic%). ]

In the above formula, M is one or both of Co and Ni. Including these elements, the magnetostriction of the material is adjusted, or induced magnetic anisotropy is obtained by a method such as heat treatment in a magnetic field. By applying a magnetic field, it is possible to realize a magnetization curve according to the application. However, when these elements are contained in a large amount, magnetostriction is extremely increased and magnetic properties are deteriorated.

M ′ is one or more elements selected from the group consisting of Nb, W, Zr, Ta, Hf, Ti, and Mo. These elements have high amorphous forming ability, and Of charges! It is an element effective for increasing the ¹ e concentration and increasing the saturation magnetic flux density. However, if these elements are contained in large amounts, a compound phase which adversely affects the magnetic properties after the heat treatment is easily formed, so it is preferable to add the elements in a range of 10 atomic% or less. The desired soft magnetic properties can be obtained relatively easily by using Zr.However, as described above, when Zr is used, a vacuum device is indispensable in the alloy heating step. When used, it is preferable that the amount used is 1.5 atomic% or less.

M "is one or more elements selected from the group consisting of V, Cr, Mn, Al, platinum group elements, Sc, Y, rare earth elements, Au, Zn, Sn, Re, and Ag; These have the effect of improving the corrosion resistance of the material ゃ abrasion resistance, adjusting magnetostriction, reducing the grain size of the Fe phase, etc. However, when the content of these elements increases, the saturation magnetic flux density When used, it is necessary to keep the usage within a certain upper limit.

Μ '"is one or more elements selected from the group consisting of C, Ge, Sb, In, As, and Be. These elements are effective elements for amorphization, and include B, P, and the like. It has the effect of helping to make the alloy amorphous and adjusting the magnetostriction, etc. However, an increase in the content of these elements causes a decrease in the saturation magnetic flux density. It is necessary to keep the usage within a certain upper limit. X is one or both of Si and A1, and these are generally well-known amorphous forming elements. When added together with B, P, etc., the amorphous forming ability of the alloy is increased. Has the effect of increasing. In addition, these elements form a solid solution in the Fe phase after the heat treatment, and have an effect of improving magnetic properties by adjusting the magnetic anisotropy and magnetostriction of the crystal phase. However, an increase in the content of these elements causes a decrease in the saturation magnetic flux density. Therefore, when used, it is necessary to keep the usage within a certain upper limit.

Therefore, the Fe-based alloy composition used for forming the soft magnetic molded body of the present invention is particularly preferably an alloy material represented by the following composition formula (2) ′.

(F Θ l- _a Ma) l O Obcd-eM ' _b B ₀ PdCu _e 11 (2)

[However, M is one or both of Co and Ni, and M, is one or more elements selected from the group consisting of Nb, W, Ta, Zr, Hf, Ti and Mo.] 0≤a≤0.05, 4≤b≤7, 5≤c≤12, 0≤d≤1.5, 0≤e≤0.5 (However, the total amount of Fe and M is 80 ~ 90 Atomic%). In addition, unavoidable impurities such as H, N, 0, S, etc. can be regarded as the same as the material composition of the present invention even if they contain the desired characteristics without deteriorating.

¾Βis · ©.

As described above, the soft magnetic molded body of the present invention is characterized in that, by rapidly cooling the Fe-based alloy composition in a molten state, a fine Fe-crystal phase (fine bccFe crystal phase) is formed in the amorphous body. After forming a ribbon in which is dispersed, if necessary, after performing a processing such as winding, the ribbon is heated to a temperature higher than the crystallization temperature of the Fe-based alloy composition, Manufactured by growing the crystal phase. Rapid cooling of the molten alloy is carried out using a single roll method, twin roll method, centrifugal quenching method, or the like.

The heat treatment for the growth of the fine Fe-crystalline phase in the ribbon or its workpiece is usually performed in the temperature range of 100-700 ° G. This heat treatment is usually performed in a vacuum or in an atmosphere of an inert gas such as hydrogen gas, nitrogen gas, or argon gas. In some cases, it may be performed in the atmosphere. However, if the alloy composition contains 2 atomic% or more of the Zr element, its oxidation becomes a problem. It is necessary to do. Also, heat treatment can be performed in a magnetic field or under stress to adjust the magnetic properties. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Example]

The alloys shown in the following examples were produced by a single roll liquid quenching method. That is, molten metal is ejected from the slit at the tip of the nozzle placed on one rotating copper roll onto the above-mentioned nozzle by the pressure of argon gas, and rapidly cooled to obtain a ribbon. The roll and nozzle are housed in a vacuum container. When preparing the ribbon, the inside of the container was evacuated in advance, and argon gas was introduced. The peripheral speed of the roll was 30 to 40 m / sec. The thickness of the ribbon produced as described above was about 20 mm. The structure of the quenched ribbon was investigated using X-ray diffraction. In addition, the toughness of the ribbon was examined in terms of whether or not it could be folded 180 ° (the case where the ribbon did not break even if it was bent 180 ° is referred to as being able to be bent tightly). The quenching operation of alloy compositions other than the alloy composition of Sample No. 10 containing 3.5 atomic% of Zr in the alloy composition was also performed in the air.

[Example 1]

The internal structure of the ribbon F e- microcrystalline phase is an amorphous phase dispersed in the state of After quenching the F e alloy compositions in accordance with the present invention, F e ₈₅ Nb ₆ B ₉ and Fe _84. ₉ This will be described by taking the Nb ₆ B ₉ Cuo. I alloy as an example.

Figure 1 is, F e ₈₅ Nb ₆ B ₉ and _{_{_{F e 84. 9 Nb 6 B}}} 9 Cu. X-ray diffraction pattern of the alloy in the quenched state. In the X-ray diffraction pattern, on the halo diffraction pattern specific to the amorphous phase, a sharp diffraction beak specific to the Fe Fe crystal phase is seen, and the ribbon is the amorphous phase and one Fe crystal. It can be seen that the phases are mixed phases. — Using the Sierra equation to estimate the grain size of the Fe Fe crystal phase from the half width of the diffraction peak of the Fe crystal phase, it was about 45 nm for the Fe ₈₅ Nb ₆ B ₉ alloy. _{_{_{F e 84. 9 N b 6}}} B 9 C u. In, the particle size could not be determined because the intensity of the diffraction peak of However, the half width of the peak is very wide, and the particle size is judged to be smaller than about 10 nm.

In other words, it can be said that by adding 0.1 atomic% of Cu, the grain size of one Fe crystal phase in the quenched state becomes fine. In addition, both of these alloys were capable of close bending (180 ° bending) in a rapid state, and had high toughness.

[Example 2]

Table 1 shows the alloy compositions, the thicknesses of the ribbons, the structure in the quenched state, and the possibility of close bending for the ribbons produced from Fe alloy compositions of various compositions. The X-ray diffraction patterns of the samples Nos. 1 to 10 revealed that the quenched state was a mixed phase of the amorphous phase and the α-Fe crystal phase. When the grain size of the Hi-Fe crystal phase was estimated from the diffraction beak of the Hi-Fe crystal phase, it was about 30-40 nm. In the case of samples Nos. 3, 8 and 1, the intensity of the diffraction peak of the α-Fe crystal phase was so low that it was not possible to determine the exact particle size. Is very wide, and the particle size is judged to be smaller than about 10 nm. It was confirmed that all of the samples Nos. 1 to 10 could be bent tightly without damage and had high toughness.

Table 1

BAJ material Alloy composition (atomic%) a-F e crystalline phase

() Particle size (〃m)

1 FessNbeBsPi 19 40

2 F 6 s4.95 Nb ₆ B ₈ PiCuo.05 21 40

3 Fe _84. sNbeBsPiCuo.! 20 10>

_{_{_{4 F e 84. 5 Nb 6}}} B 8 PiC o. 5 22 40

_{_{_{5 Fe 8 4Nb 6. 5 B}}} 6. 3 P 3 Cu 0. 2 17 40

_{_{7 F e 85. I 5 Nb}} 5. 5 B 8. 25 Cu 0. I 22 35

8 (Feo.99Nio.01) 83.gNbeBsPiCUo.1 19 10>

_{_{9 Fe 84 Nb 5 .5M01B9.5 17 40}} 0 Fe 86 Z r 3. 5 Nb 3. 5 B 6 Cui 20 10>

[Example 3]

A wound core having an inner diameter of about 5 mm and an outer diameter of about 6 mm was formed using the ribbon produced in Example 2, and heat-treated at 650 ° C. for 5 minutes in a vacuum. Winding was performed on the wound core after heat treatment, and the permeability (m), BH curve, and core loss were measured. The permeability was measured at an applied magnetic field of 5 mOe and a frequency of 1 kHz. The saturation magnetic flux density (B s) was calculated from the AC magnetization curve at a maximum magnetic field of 10 Oe and a frequency of 1 OHz. The core loss was measured at a maximum magnetic flux density of 1.4 T and a frequency of 5 OHz. Table 2 shows the measurement results of permeability, saturation magnetic flux density, and core loss. Table 2 Sample Alloy composition (atomic%) Permeability Saturation magnetic flux Core loss

/ (1kHz) Particle size (zm) W (W / kg)

1 Fe ₈₅ Nb ₆ B ₈ P ₁ 19700 1.57-1.61 0.14

2 Fe _84. GsNbeBeP iCuo. ₀₅ 30 600 1.59-1.63 0.12

3 Fe _84. SNbeBsP iCuo.! 40800 1.57-1.61 0.11

_{_{_{4 F e 84. 5 Nb 6}}} B 8 PiCuo. 5 17200 1.59- 1.62 0.14

_{_{_{5 F e 84 Nb 6. 5}}} B 6. 3 P 3 Cu 0. 2 22600 1.50-1.55 0.13

_{_{_{6 F e 84 Nb 6. 5}}} B 8. 5 Ci 25800 1.53-1.56 0.13

_{_{7 F e 85. IsNb 5.}} 5 B 8. 25 Cu 0. I 10900 1.60- 1.65 0.14

_{_{8 (Fe 0. 99 Nio.oi)}} 83. sNbeBsPi Cuo. Χ 23600 1.53- 1.56 0.15

_{_{_{9 Fe 8 4Nb 5. 5 MoiB}}} 9. 5 21000 1.54- 1.55 0.14 0 Fe 86 Z r 3. 5 Nb 3. From sBeCux 61000 1.54 0.07 of Table 2 results, thin obtained from Fe-based alloy compositions of the present invention After heat treatment, the band was confirmed to have a magnetic permeability of 10000 or more at a frequency of 1 kHz, a saturation magnetic flux density of 1.5 T or more, and a core loss at a frequency of 50 Hz of 0.15 W / kg or less. Was.

[Example 4]

Nb content is 6 atomic%, B content is 8 ~; I 5 atomic%, P content is 0 or 1 atomic%, Cu content is 0-1 atomic%, and the balance of Fe is made of alloy ribbon. And 650 in vacuum. C, the magnetic permeability at 1 kHz after the heat treatment for 5 minutes was measured. Changes in the magnetic permeability of these alloys with respect to the B content and the B + P content are shown in FIGS. 2 and 3. When the Nb content was 6 at%, a mixed phase of amorphous and α: -Fe crystals was obtained at a B + .P content of 10.5 at% or less in the quenched state. From Fig. 2, it can be seen that in alloys that do not contain P, a high permeability of 10,000 or more has a B content of 8 to 15 at%, and a superior magnetic permeability of 20000 or more has a B content of 9 to 12 at%. It can be seen that the amount can be obtained.

Also, from Fig. 3, in an alloy containing 1 atomic% of P, a high magnetic permeability of 10,000 or more has a B + P content of 8 atomic% or more, that is, a B content of 7 atomic% or more, and an additional 20 000 or more. It can be seen that better magnetic permeability can be obtained with a B + P content of 9 atomic% or more, that is, a B content of 8 atomic% or more.

In alloys with higher Nb content, or alloys containing Zr and Hf with higher amorphous formation ability than Nb, the amorphous phase is stable even at lower B concentration It is considered that a high magnetic permeability can be obtained because of the formation. Conversely, alloys with a lower Nb content or alloys containing W, Ta, Ti, and Mo, which have lower amorphous forming ability than Nb, can be regarded as amorphous amorphous even at higher B concentrations. It is considered that a mixed phase state of the crystal is obtained. It is considered that the magnetic properties deteriorate at a B concentration exceeding 15 atomic% mainly because boride of Fe is formed after the heat treatment. Therefore, in the present invention, the B content is set to 0.5 ^ 15 atomic%. %, It can be said that the magnetic characteristics can be improved. Also, considering that alloys containing Zr, Hf, etc., which have higher amorphous forming ability than Nb, can obtain high amorphous forming ability and excellent magnetic properties even at a lower B content, the present invention It is considered that by setting the B content to 5 to 12 atomic%, particularly excellent magnetic properties can be obtained.

[: Example 5]

Figure 4 shows the X-ray diffraction pattern of the alloy ribbon in the quenched state when the value of x was changed in the alloy composition Fe ₈₄ — xNbsBsPiCUx. In the X-ray diffraction pattern, on the halo diffraction pattern peculiar to the amorphous phase, a sharp diffraction peak peculiar to the single Fe crystal phase shown by 〇 is seen, and the ribbon is the same as the amorphous phase. It turns out that it is a mixed phase of a crystal phase. In the case of Fe ₈₄ .gNbeBePiCuo.i, the peak of the Hi-Fe crystal phase is very small and cannot be clearly observed because the grain size of the Hi-Fe crystal phase has been reduced to about 10 nm or less. Figure 5 shows the change in the magnetic permeability at 1 kHz with respect to the Cu content of these ribbons after heat treatment at 650 ° C for 5 minutes in vacuum.

From FIG. 5, it can be seen that a high magnetic permeability of 10,000 or more can be obtained by reducing the Cu content to 1 atomic% or less. Further, reduce the Cu content to 0.5 atomic% or less. This indicates that a higher magnetic permeability of 17 000 or more can be obtained. That is, in the present invention, the magnetic properties can be further improved by reducing the Cu content to 1 atomic% or less, more preferably 0.5 atomic% or less. .

[Example 6]

F e ₈₄ prepared in Example _{_{_{1. 9 N b 6 B 8}}} C u. i Alloy ribbon, produced in Example 2

(No. 3) and the alloy ribbon, Fe ₈₄ the newly-made _{_{_{_{work. 9 Nb 6 B 8. 5}}}} P 0. 5 Cu 0. Fe 84. 9 Nb 6 B 7. 5 Pi. 5 Cu 0. I, the _{_{_{F e 8 4. 9 Nb 6 B}}} 7 P 2 Cuo. i X -ray diffraction pattern in the rapid cooling of the alloy thin strap ribbon shown in Figure 6. In the X-ray diffraction pattern, a sharp diffraction peak peculiar to the --Fe crystal phase is shown on the halo diffraction pattern peculiar to the amorphous phase. It can be seen that this is a mixed phase of the crystal phase. In Fe ₈₄ .gNbeBsPiCuo.i, as described above, the peak of the Fe crystal phase is very small and cannot be clearly observed because the grain size of the Fe crystal phase is becoming finer. Fig. 7 shows the change in the magnetic permeability at 1 kHz after the heat treatment of these ribbons in vacuum at 650 ° C for 5 minutes with respect to the P content.

From FIG. 7, it can be seen that a high magnetic permeability of 10,000 or more can be obtained in any of the alloys. Further, it can be seen that by setting the P content to 1.5 atomic% or less, a better magnetic permeability of 19,000 or more can be obtained. That is, the magnetic properties can be further improved by reducing the P content to 1.5 atomic% or less.

[Industrial applicability]

According to the present invention, high saturation magnetic flux density of 1.5 T or more, high magnetic permeability of 10,000 or more, and low core loss of 0.15 W / kg or less at a frequency of 50 Hz, which could not be achieved with conventional practical alloys Can be obtained. Therefore, the soft magnetic molded article of the present invention is suitable as a material for forming a magnetic core, such as a transformer, a choke coil, and a motor, for which further miniaturization, higher performance, and higher efficiency are desired. Further, the ribbon for producing a soft magnetic molded article of the present invention has a high toughness and therefore also has a good additivity, is easily applied to industrial applications, and its effect is remarkable. The scope of the claims

1. Rapid solidification of a molten Fe-based alloy composition with an Fe content of 80-90 at.% In the molten state to form a single-crystal Fe phase with an average particle size in the range of 1-43 nm in the amorphous phase. Manufacturing a ribbon having a mixed phase structure formed in a dispersed state and capable of bending at 180 °, and heating the ribbon to a temperature higher than the crystallization temperature of the Fe phase Soft core with a permeability of 10,000 or more at a frequency of 1 kHz, a saturation magnetic flux density of 1.5 T or more, and a core loss of 0.15 W / kg or less at a frequency of 50 Hz. A method for producing a magnetic molded body.

2. The method for producing a soft magnetic molded article according to claim 1, wherein the average particle size of the Hi-Fe crystal phase in the ribbon is in the range of 1 to 40 nm.

3. The method for producing a soft magnetic molded body according to claim 1, wherein the ribbon is produced to have a thickness of 5 to 100 m.

4. The soft magnetic material according to any one of claims 1 to 3, wherein at least one of winding, punching, etching, surface polishing, and slitting is performed before heating the ribbon. A method for producing a molded article. '

5. The Fe-based alloy composition comprises 1 to: 0 atomic% of L] ^ ゎ, W, Ta, Zr,: one or more elements selected from the group consisting of Bf, Ti and Mo. 5 to 25 atomic% of B, and 0.01 to 5 atomic% of uranium, Cu, V, Cr, Mn, Al, platinum group element, Sc, Y, rare earth element, Au, Zn, Sn, Re, The soft magnetism according to any one of claims 1 to 4, comprising one or more elements selected from the group consisting of Ag, C, Ge, Sb, In, As, Be, and Si. Molded body production ο

Claims

6. The Fe-based alloy composition is one or more elements selected from the group consisting of 2 to 10 atomic percent Nb and Hf, 0.5 to 25 atomic percent 8, and 0.01 to 5 atomic percent. The method for producing a soft magnetic molded article according to any one of claims 1 to 4, wherein the method comprises one or more elements selected from the group consisting of 1 ^ 0, P, Cu, and C. . '

7. The method for producing a soft magnetic molded article according to claim 1, wherein the Fe content of the Fe-based alloy composition is at least 82 atomic%.

8. A magnetic core composed of an Fe-based alloy composition with an Fe content of 80 to 90 atomic%, having a permeability of 10,000 or more at a frequency of 1 kHz, a saturation magnetic flux density of 1.5 T or more, and a frequency of 50 Hz. Soft magnetic compact with loss of 0.15 W / kg or less.

9. One or more elements selected from the group consisting of 1 to 10 atomic% of 13, W, Ta, Zr, Hf, Ti and Mo, wherein the Fe-based alloy composition has 1 to 10 atomic%, 0.5 to 25 atomic % B, and 0.01 to 5 atomic%? , Cu, V, Cr, Mn, Al, chromium, Sc, Y, rare earth, Au, Zn, Sn, Re, Ag, C, Ge, Sb, In, As, Be, and Si 9. The soft magnetic molded article according to claim 8, comprising one or more elements selected from the group.

10. The Fe-based alloy composition is one or more elements selected from the group consisting of: 2 to: 0 atomic%] ^ 1) and Hf; 0.5 to 25 atomic% of B; 10. The soft magnetic molded body according to claim 8, which comprises one or more elements selected from the group consisting of P, Cu, and C].

11. The soft magnetic compact according to any one of claims 8 to 10, wherein the Fe content of the Fe-based alloy composition is at least 82 atomic%.

12. A wound core formed by winding the soft magnetic molded body according to any one of claims 8 to 11 formed as a thin strip having a thickness of 5 to 100 m.

13. Rapid solidification of a molten Fe-based alloy composition with an Fe content ratio of 80 to 90 atomic%, and a single Fe crystal phase with an average particle size in the range of 1 to 42 nm dispersed in the amorphous phase. A method for producing a ribbon of a Fe-based alloy composition having a mixed phase structure formed in a state and capable of bending at 180 ° and having a thickness of 5 to 100 μm.

14. The method for producing a ribbon according to claim 13, wherein the average particle size of the crystal phase of Fe in the ribbon is in the range of 1 to 4 Onm.

15. an Fe-based alloy composition of 1 to 2; one or more elements selected from the group consisting of L at. 0 atomic% of Nb, W, Ta, Zr, Hf, Ti and Mo; 2 5 at% B, and 0.01 to 5 at%? , Cu, V, Cr, Mn, Al, platinum group elements, Sc, Y, rare earth elements, Au, Zn, .Sn, Re, Ag, C, Ge, Sb, In, As, Be, and Si 15. The method for producing a ribbon according to claim 13 or 14, comprising one or more elements selected from the group.

16. The Fe-based alloy composition is one or more elements selected from the group consisting of 2 to 10 atomic% of Nb and Hf, 0.5 to 25 atomic% of 8, and 0.01 to 5 atomic%. 15. The method for producing a ribbon according to claim 13 or 14, comprising one or more elements selected from the group consisting of ^ 10, P, Cu, and C.

17. The method for producing a ribbon according to any one of claims 13 to 16, wherein the Fe content of the Fe-based alloy composition is 82 atomic% or more.

18. A Fe-based alloy composition with a Fe content of 80 to 90 atomic%, and an α-Fe crystalline phase with an average particle size in the range of 1 to 4.2 nm formed in a dispersed state in the amorphous phase. A ribbon with a mixed phase structure and a thickness of 5 to 100 m of an Fe-based alloy composition that can be bent at 180 °.

19. The ribbon according to claim 18, wherein the average particle size of the Hi-Fe crystal phase is in the range of 1 to 4 Onm.

20. The Fe-based alloy composition is from 1 to 10 atomic% of one or more elements selected from the group consisting of 10, W, Ta, Zr, Hf, Ti and Mo, 0.5 to 25. Atomic% B, and 0.01 to 5 Atomic%! ³ , consisting of Cu, V, Cr, Mn, Al, platinum group elements, Sc, Y, rare earth elements, Au, Zn, Sn, Re, Ag, C, Ge, Sb, In, As, Be, and Si 20. The ribbon according to claim 18 or 19, comprising one or more elements selected from the group.

21. One or more elements selected from the group consisting of 2 to 10 atomic%] ^ 13 and Hf, Fe-based alloy composition, 0.5 to 25 atomic% B, and 0.01 to 5 atomic%. 20. The ribbon according to claim 18 or 19, wherein the ribbon comprises one or more elements selected from the group consisting of atomic%], P, Cu, and C.

22. The ribbon according to any one of claims 19 to 21, wherein the Fe content of the Fe-based alloy composition is 82 atomic% or more.