JP2000156313A - LOW IRON LOSS Fe BASED SOFT MAGNETIC ALLOY CORE - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high permeability, low iron loss and high saturation flux density by having composition expressed by a specific equation, having fine crystal particles of bccFe with a specific average crystal particle size or less in at least 50% or more of the composition, and depositing amorphous phase after changing this fine crystal particles into an amorphous single-phase structure. SOLUTION: An Fe based soft magnet alloy core comprises a composition expressed by (Fe1-aQa)bBxMyZnz, where Q is Co and/or Ni, M is one or more of Ti, Zr, Hf, V, Nb, Ta, Mo and W, a <= 0.05, 80 atomic percent <= b, 5 atomic percent <= x <= 12.5 atomic percent, 5 atomic percent <= y <= 7.5 atomic percent, 0.025 atomic percent <= z <= 0.200 atomic percent, at least more than 50% of the composition has fine crystal particles of bccFe at about 100 nm or less of average crystal particle size, and the remainder comprises amorphous alloy phase. The fine crystal particles in bccFe are deposited by heating the amorphous phase up to crystallization temperature or more and then cooling it, after quenching alloy melt with above mentioned composition into substantially amorphous single-phase structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Fe-based soft magnetic alloy core used for a transformer, a choke coil and the like, and more particularly to a magnetic core having a high saturation magnetic flux density, excellent soft magnetic characteristics and low iron loss.

[0002]

2. Description of the Related Art The characteristics generally required of soft magnetic alloys used for transformers, choke coils, and the like are as follows. High saturation magnetic flux density. High permeability. Low coercive force. Easy to obtain thin shape.

[0003] Therefore, in the production of soft magnetic alloys for transformers and choke coils, materials have been studied in various alloy systems from these viewpoints. Conventionally, for the above-mentioned applications, crystalline alloys such as Sendust (registered trademark), Permallo (registered trademark) a, and silicon steel have been used, and recently, Fe-based and Co-based amorphous alloys have also been used. It is becoming.

[0004]

However, a transformer,
In the case of a choke coil, further downsizing is required in accordance with downsizing of an electronic device. Therefore, a magnetic material with higher performance is desired. However, the above sendust has excellent soft magnetic properties, but has a saturation magnetic flux density of about 1.1T.
(Tesla) has a low defect. Permalloy also has a low saturation magnetic flux density of about 0.8 T in an alloy composition having excellent soft magnetic properties. Silicon steel has a high saturation magnetic flux density but a low soft magnetic property. There is a disadvantage that the characteristics are inferior.

On the other hand, among the amorphous alloys, the Co-based alloy is excellent in soft magnetic properties, but has an insufficient saturation magnetic flux density of about 1.0T. In addition, Fe-based alloys have a high saturation magnetic flux density, and 1.5 T or more can be obtained, but their soft magnetic properties are insufficient. Further, the thermal stability of the amorphous alloy is not sufficient, and there are still unsolved aspects. As described above, it is difficult to combine high saturation magnetic flux density with excellent soft magnetic characteristics.

An important characteristic of a soft magnetic alloy for a transformer is that the core loss is small and the saturation magnetic flux density is high. However, the iron loss of a silicon steel sheet which has been most widely used for transformers is 1.0 w /
kg (at 1.7 T, 50 Hz) and the saturation magnetic flux density is 2.0 T. Therefore, although the saturation magnetic flux density is high, the iron loss needs to be further reduced. Further, in the case of Fe-based amorphous alloys for transformers which have been conventionally used for some applications, iron loss is 0.25 w / kg (1.4 T,
(At 50 Hz), since the saturation magnetic flux density is 1.56 T, there is a problem that it is desired to further reduce iron loss and increase the saturation magnetic flux density.

The inventors of the present invention have proposed, as an advanced alloy of the above alloy, Japanese Patent Publication No. 7-65145,
No. 93249, etc., an amorphous alloy phase and bcc
An Fe-based soft magnetic alloy having a structure mainly composed of Fe fine crystal grains, having a saturation magnetic flux density of more than 1.5 T and a magnetic permeability of more than 10,000 is provided.

[0008] One of the alloys according to this patent application is a high saturation magnetic flux density alloy having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M _1y where Q is one or both of Co and Ni;
₁ is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and includes one or both of Zr and Hf; ≦ 0.0
5, b ≦ 93 at%, x = 5.0 to 8 at%, y = 4 to 9
Atomic%.

Another one of the alloys according to the patent application is a high saturation magnetic flux density alloy having a composition represented by the following formula. Fe _b B _x M _1y where b ≦ 93 at%, x = 5 to 8 at%, y = 4 to 9 at%. As a result of further research on the alloy of the composition system, the present inventors have found that, by adding a small amount of Zn to the Fe-based soft magnetic alloy of the composition system, the soft magnetic properties are improved, and the iron loss is improved. And found that it is possible to provide a magnetic core with significantly reduced iron loss by improving the soft magnetic properties by adjusting the composition ratio of Zr and Nb to a specific range, The present invention has been reached.

An object of the present invention is to develop the Fe-based soft magnetic alloy of the above patent application to further increase magnetic permeability, significantly reduce iron loss, have a high saturation magnetic flux density, have high mechanical strength and high thermal stability. An object of the present invention is to provide a magnetic core made of a low iron loss Fe-based soft magnetic alloy having both properties. Further, the present invention reduces the iron loss to 0.1.
5 w / kg (at 1.4 T, 50 Hz) or less, the saturation magnetic flux density can be 1.5 T or more, and the low iron loss F with little change over time in magnetic properties even when left in a heated state for a long time.
It is intended to provide an e-based soft magnetic alloy magnetic core.

[0011]

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a composition represented by the following formula, and at least 50% or more of the structure has an average crystal grain size. After the bccFe fine crystal grains having a diameter of 100 nm or less are formed, and the remainder is formed of an amorphous alloy phase, the bccFe fine crystal grains rapidly cool the alloy to form a substantially amorphous phase single phase structure. Characterized in that the crystalline phase is heated to a temperature higher than the crystallization temperature, then cooled and precipitated.
It is characterized by being made of an e-based soft magnetic alloy. _{(Fe 1-a Q a)} b B x M y Zn z where, Q is Co, a or Ni,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and a, b, x, y, and z indicating the composition ratio are a ≦ 0.05, 80 atomic% ≦
b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.
5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%.

In order to solve the above-mentioned problem, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the preceding claim. It may be made of an alloy. Fe _{b B x} M _y Zn _z However, b showing the composition ratio, x, y, z are 80 atomic% ≦
b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.
5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the above claim. It may be made of an alloy. (Fe _1-a Q _a ) _b B _x M
_y Zn _z M ' _u, where M' is one or more elements selected from Cr, Ru, Rh, and Ir, and represents a,
b, x, y, z and u are a ≦ 0.05, 80 atomic% ≦ b,
5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%, and u ≦ 5 atomic%.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the above claim. It may be made of an alloy. Fe _{b B x} M _y Zn _z
M'u, where M 'is one or more elements selected from Cr, Ru, Rh, and Ir, and b, which indicates a composition ratio,
x, y, z and u are 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.
5 atomic%, 5 atomic% ≦ y ≦ 7 atomic%, 0.025 atomic%
≦ z ≦ 0.2 atomic% and u ≦ 5 atomic%.

In order to solve the above-mentioned problems, the low iron loss Fe-based soft magnetic alloy core of the present invention contains Fe, Zr, Nb and B, and further contains Zn.
% Or more is made of fine crystal grains of bccFe having an average crystal grain size of 100 nm or less, and the remainder is made of a low iron loss F made of an amorphous alloy.
It is made of an e-based soft magnetic alloy.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the above claim. It may be made of an alloy. _{(Fe 1-a Q a)} b Zr c
Nb _d B _x Zn _z where a, b, c, d, x, and z indicating the composition ratio are a ≦
0.05, 80 at% ≦ b, 1.5 at% ≦ c ≦ 2.5 at%, 3.5 at% ≦ d ≦ 5.0 at%, 5 at% ≦ x ≦ 1
2.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%, and 5.0 atomic% ≦ c + d ≦ 7.5 atomic%, 1.5 / 6 ≦
c / (c + d) ≦ 2.5 / 6.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy magnetic core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the preceding claim. It may be made of an alloy. _{Fe b Zr c Nb d B x} Z
_nz where b, c, d, x and z indicating the composition ratio are 80 atomic%.
≦ b, 1.5 atomic% ≦ c ≦ 2.5 atomic%, 3.5 atomic% ≦ d
≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.0
25 atomic% ≦ z ≦ 0.2 atomic%, and 5.0 atomic% ≦ c
+ D ≦ 7.5 atomic%, 1.5 / 6 ≦ c / (c + d) ≦ 2.
5/6.

In order to solve the above problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the preceding claim. It may be made of an alloy. _{(Fe 1-a Q a)} b Zr c
Nb _d B _x Zn _z M ′ _u where M ′ is one or two or more elements selected from Cr, Ru, Rh, and Ir, and indicates a,
b, c, d, x, z and u are a ≦ 0.05 and 80 atomic% ≦
b, 1.5 atomic% ≦ c ≦ 2.5 atomic%, 3.5 atomic% ≦ d ≦
5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.02
5 atomic% ≦ z ≦ 0.2 atomic%, u ≦ 5 atomic%, and 5.
0 atomic% ≦ c + d ≦ 7.5 atomic%, 1.5 / 6 ≦ c / (c
+ D) ≦ 2.5 / 6.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention has a low iron loss Fe-based soft magnetic core having a composition represented by the following formula instead of the alloy composition described in the preceding claim. It may be made of an alloy. Fe _b Zr _c Nb _{d B x}
Zn _z M ′ _u where M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, and indicates a composition ratio b,
c, d, x, z, and u are 80 atomic% ≦ b, 1.5 atomic% ≦
c ≦ 2.5 at%, 3.5 at% ≦ d ≦ 5.0 at%, 5
Atomic% ≦ x ≦ 12.5 atomic%, 0.025 atomic% ≦ z ≦
0.2 atomic%, u ≦ 5 atomic%, and 5.0 atomic% ≦ c +
d ≦ 7.5 atomic%, 1.5 / 6 ≦ c / (c + d) ≦ 2.5
/ 6.

In order to solve the above-mentioned problems, a low iron loss Fe-based soft magnetic alloy core according to the present invention is characterized in that, in the low iron loss Fe-based soft magnetic alloy core described above, a change in iron loss caused by heating at 200 ° C. for 500 hours Rate is 10% or less, the saturation magnetic flux density is 1.5T or more, and the iron loss when applying a magnetic flux of 1.4T at a frequency of 50 Hz is 0.15 W / kg or less.

In the low iron loss Fe-based soft magnetic alloy core described above, b, c, d, x, y and z indicating the composition ratio are 83
Atomic% ≦ b, 5.7 ≦ c + d ≦ 6.5 atomic%, 1.5 / 6
≦ c / (c + d) /≦2.5/6, 6 atomic% ≦ x ≦ 9.5
Atomic% may be used.

In the present invention, it is preferable that the low iron loss Fe-based soft magnetic alloy has a fracture strain of 10 × 10 ⁻³ (1.0 × 10 ⁻² ) or more. In the present invention, the annular body formed from the low iron loss Fe-based soft magnetic ribbon is
It is preferable to use one or two or more sheets. In the present invention, it is preferable that the low-iron-loss Fe-based soft magnetic alloy is formed of an annular ring formed by winding a thin ribbon.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The Fe-based soft magnetic alloy core of the present invention is realized by, for example, a toroidal ring core. Such a magnetic core is manufactured by manufacturing a ribbon of a low iron loss Fe-based soft magnetic alloy having a composition described below by a quenching method described below, and then press-punching the obtained ribbon to obtain a ring-shaped one. This ring is formed by laminating the required number of pieces, or the above-mentioned ribbon is wound to form an annular shape, and the magnetic core is coated with a resin, for example, with an epoxy resin, or sealed in a resin case to protect the insulation, It is obtained by winding. Further, in order to realize an EI core type magnetic core, the above-mentioned ribbon is stamped out into an E type or an I type so as to produce the required number of E type and I type thin pieces. It can be obtained by laminating flakes or I-shaped flakes to produce an E-shaped core and an I-shaped core, and joining them. The E-type core and the I-type core are covered with a resin, for example, with epoxy resin, or inserted into a resin case to insulate the necessary parts, and after winding, the side of the E-type magnetic core and the I part By joining the side portions of the mold magnetic core, an Fe-based soft magnetic alloy core is obtained. In addition,
The magnetic core is not limited to a combination of an E-type core and an I-type core, but may be an E-type core and an E-type core, a U-type core and an I-type core,
A magnetic core made of any combination of the mold core and the U-shaped core may be used.

FIGS. 1 and 2 each show one form of a toroidal transformer structure. In the structure of the form shown in FIG. 1, the upper and lower cases 2 are divided into a hollow annular upper case 1 and a lower case 2. It is configured to house a magnetic core 3 in which a plurality of thin rings of a low iron loss Fe-based soft magnetic alloy, which will be described later, are stacked, and in the configuration shown in FIG. A transformer is formed by winding a thin ribbon 5 of a low iron loss Fe-based soft magnetic alloy and accommodating a magnetic core 6 which is entirely covered with a resin. The upper case 1 and the lower case 2 may be used as appropriate, and it is a matter of course that the magnetic core may be constituted only by resin coating.

FIG. 3 shows the low iron loss Fe according to the present invention.
1 shows an embodiment in which a soft magnetic alloy core is applied to a common mode choke coil. As shown in FIG. 3, the structure of this embodiment is composed of a magnetic core 1 formed by winding a thin ribbon of a low iron loss Fe-based soft magnetic alloy having a composition described later and being coated with a resin.
2 and three windings 13 wound therearound, respectively, and a bobbin 14 mounted on a magnetic core 12 for three phases, and is applied to a noise filter or the like.

More specifically, as an example of the low iron loss Fe-based soft magnetic alloy constituting the ribbon, at least 50% or more of the structure has an average crystal grain size of 100% or more.
nm or less of bccFe fine crystal grains, and the remainder is composed of an amorphous alloy phase. The fine crystal grains of bccFe are quenched from a molten alloy having a composition described later to form a substantially amorphous phase single phase structure. Examples thereof include those in which the amorphous phase is heated to a crystallization temperature or higher, then cooled and precipitated.
_{(Fe 1-a Q a)} b B x M y Zn z where, Q is Co, either or both the Ni, M
Is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and a ≦ 0.0.
5, 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5
Atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦ z ≦ 0.5
It is 200 atomic%.

Another embodiment of the low iron loss Fe-based soft magnetic alloy used in the present invention is a composition represented by the above-described composition in which the element Q is omitted, that is, a composition represented by Fe _b B _x M _y Zn _z. It has. In this composition formula, the content ratio of each element is the same as that in the above composition formula.

Another form of the low iron loss Fe-based soft magnetic alloy used in the present invention has a composition represented by the following formula, and at least 50% or more of the structure is composed of fine bccFe grains having an average grain size of 100 nm or less. The remainder is composed of an amorphous alloy phase, and the fine crystal grains of bccFe are quenched from a molten alloy having a composition represented by the following formula to form a substantially amorphous phase single-phase structure. Is heated to a temperature higher than the crystallization temperature and then cooled to precipitate. (Fe _1-a Q _a ) _{b
B x M y Zn z M '} u where Q is Co, a one or both of Ni, M
In Ti, Zr, Hf, V, Nb, Ta, Mo, W
M ′ is one or more elements selected from
One or more elements selected from Cr, Ru, Rh, and Ir, a ≦ 0.05, 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic % ≦ y ≦ 7.5 at%, 0.025 at% ≦ z ≦ 0.200 at%, and u ≦ 5 at%.

[0029] Other forms of low iron loss Fe-based soft magnetic alloy used in the present invention, in the composition described previously, the composition formula is omitted element Q, i.e., in _{Fe b B x M y Zn z} M 'u It has the composition shown. In this composition formula, the content ratio of each element is the same as that in the composition formula described above.

Next, another embodiment of the low iron loss Fe-based soft magnetic alloy used in the present invention contains Fe, Zr, Nb, and B, and further contains Zn to form at least 50% of the structure.
% Or more is made of fine crystal grains of bccFe having an average crystal grain size of 100 nm or less, and the balance is made of an amorphous alloy.
An e-based soft magnetic alloy can be exemplified.

As another specific embodiment of the low iron loss Fe-based soft magnetic alloy used in the present invention, a composition represented by the following formula is used in place of the above composition formula, and at least 50% or more of the structure is averaged. Bcc Fe fine crystal grains having a crystal grain size of 100 nm or less, the remainder consisting of an amorphous alloy phase,
The fine crystal grains of Fe were formed by quenching an alloy (melt) having a composition described later to form a substantially single-phase structure of an amorphous phase. It may be something. _{(Fe 1-a Q a)} b Zr x Nb y B t Zn z where, Q is Co, a or Ni,
A, b, x, y, t, and z indicating the composition ratio are a ≦ 0.05,
80 atomic% ≦ b, 1.5 atomic% ≦ x ≦ 2.5 atomic%, 3.5
Atomic% ≦ y ≦ 5.0 atomic%, 5 atomic% ≦ t ≦ 12.5 atomic%, 0.025 atomic% ≦ z ≦ 0.200 atomic%,
5.0 atomic% ≦ x + y ≦ 7.5 atomic%, 1.5 / 6 ≦ x /
(X + y) ≦ 2.5 / 6.

[0032] Another one specific embodiment of a low iron loss Fe-based soft magnetic alloy of the present invention is the composition described previously, the composition formula is omitted element Q, _{i.e., Fe b Zr x Nb y B} t Zn It has the composition shown by _z . In this composition formula, the content ratio of each element is the same as that in the above composition formula.

Another specific embodiment of the low iron loss Fe-based soft magnetic alloy of the present invention has a composition represented by the following formula, and at least 50% or more of the structure has a fine grain size of bccFe having an average crystal grain size of 100 nm or less. The fine crystal grains of bccFe are quenched by rapidly cooling an alloy (melt) having a composition to be described later to form a single-phase structure of substantially amorphous phase, and then form the amorphous phase. The solid phase is heated to a temperature higher than the crystallization temperature, then cooled and precipitated. (Fe _1-a Q _a ) _b Zr
_{x Nb y B t Zn z M} 'u where Q is Co, a or Ni,
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, and indicates a, b, x,
y, t, z and u are a ≦ 0.05, 80 atomic% ≦ b, 1.5
Atomic% ≦ x ≦ 2.5 atomic%, 3.5 atomic% ≦ y ≦ 5.0 atomic%, 5 atomic% ≦ t ≦ 12.5 atomic%, 0.025 atomic%
≦ z ≦ 0.200 at%, u ≦ 5 at%, 5.0 at% ≦ x + y ≦ 7.5 at%, 1.5 / 6 ≦ x / (x +
y) ≦ 2.5 / 6.

[0034] Another one specific embodiment of the soft magnetic alloy of the present invention is the composition described previously, the composition formula is omitted element Q, _i.e., in _{Fe b Zr x Nb y B t} Zn z M 'u It has the composition shown. In this composition formula, the content ratio of each element is the same as that shown in the above composition formula.

The low iron loss Fe-based soft magnetic alloy having the above-described composition
A step of quenching an alloy having a composition to be described later from a molten metal to obtain an amorphous alloy ribbon or an amorphous alloy powder or an amorphous alloy lump containing an amorphous single phase or partially crystalline, and an amorphous alloy lump; Is usually obtained by a step of obtaining a thin film by a vapor phase quenching method such as a sputtering method or a vapor deposition method, and a heat treatment step of heating the resultant obtained in these steps to precipitate fine crystal grains. I can do it. However,
In the alloy composition, Zn is more likely to evaporate and disappear than other elements. Therefore, as described in detail later, the amount of Zn to be added when preparing a molten metal is set to be larger than the range of the above composition formula. It is necessary to keep. The product obtained by the quenching method described above may be in the form of a ribbon, powder, or thin film. The obtained product is formed or machined into a desired shape, and then heat-treated. Of course.

B is always added to the soft magnetic alloy having the above composition. B has the effect of increasing the ability of soft magnetic alloys to form an amorphous phase, the effect of increasing the thermal stability of Fe-M (= Zr, Hf, Nb, etc.)-Based microcrystalline alloys, and the effect of becoming a barrier to crystal grain growth. This has the effect of leaving a thermally stable amorphous phase at the grain boundaries. As a result, in the heat treatment step described later, 40
To obtain a structure mainly composed of crystal grains having a fine body-centered cubic structure (bcc structure) having a particle size of 100 nm or less (specifically, 30 nm or less) which does not adversely affect magnetic properties under a wide range of heat treatment conditions of 0 to 750 ° C. Can be. The content of B is
5 atom% or more and 12.5 atom% or less are preferable, more preferably 6 atom% or more and 9.5 atom% or less, most preferably 8 atom% or more and 9.0 atom% or less. is there.

In addition, if necessary, Y, La, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
y, Ho, Er, Tm, Yb, Lu, Cd, In, S
n, Pb, As, Sb, Bi, Se, Te, Li, B
The magnetostriction of the soft magnetic alloy can be adjusted by adding elements such as e, Mg, Ca, Sr, and Ba. Note that A
Elements such as 1, Si, C and P having an ability to form an amorphous phase may be contained within a range that does not degrade the properties of the alloy of the present invention. Therefore, the content of these elements is about 1 atomic% or less. Is preferred. In addition, as unavoidable impurity elements such as H, N, O, and S, the content may preferably be 0.1 atomic% or less to the extent that desired characteristics are not deteriorated.

With respect to Ti, Zr, Hf, V, Nb, Ta, Mo, and W represented by M in the soft magnetic alloy having the above-described composition, in order to easily obtain an amorphous phase, an amorphous forming ability is required. It should preferably contain high Zr, Hf, Nb. Further, some of Zr, Hf, and Nb can be replaced with Ti, V, Ta, Mo, and W among the other group 4A to 6A elements of the periodic table.

Although Zr, Nb, etc., hardly form a solid solution in bccFe by nature, the molten alloy is rapidly cooled to become amorphous and then crystallized by a heat treatment to obtain Zr.
Can super-saturate Nb or the like in bccFe and adjust the amount of the solid solution to reduce the magnetostriction. That is, the amount of solid solution of Zr and Nb can be adjusted under the heat treatment condition, whereby the magnetostriction can be adjusted and the value can be reduced. Therefore, in order to obtain a low magnetostriction, it is necessary to obtain a fine crystal structure under a wide range of heat treatment conditions. As described above, it is difficult to obtain a fine crystal structure under a wide range of heat treatment conditions by adding B. It has both magnetostriction and small crystal magnetic anisotropy, resulting in good magnetic properties.

In order to reduce iron loss among the above-mentioned additional elements, Zr and N among the M elements are particularly preferable.
b is important, and Zr and Nb
Is particularly effective to set the ratio of
And when Nb is mainly added, the total amount of these is
The relationship of 5 ≦ (Zr content + Nb content) ≦ 7.5 is preferable, and the range of 5.7 ≦ (Zr content + Nb content) ≦ 6.5 is more preferable. Further, it is preferable that the value of (Zr content) / (Zr content + Nb content) be in the range of 1.5 / 6 to 2.5 / 6. This relationship is expressed by an equation: 1.5 /
6 ≦ (Zr content) / (Zr content + Nb content) ≦
It becomes 2.5 / 6. Also, within the range of this relational expression,
(Zr content) / (Zr content + Nb content) = 2/6
Is most preferred.

Further, the above composition has Cr, Ru, Rh, Ir
Is added as needed to improve the corrosion resistance. However, in order to keep the saturation magnetic flux density high, the addition amount of these elements is preferably set to 5 atomic% or less. Considering all aspects of iron loss and iron loss, a content of 1 atomic% or less is more preferable.

The fact that a fine crystal structure can be obtained by partially crystallizing an Fe—M (= Zr, Hf) -based amorphous alloy by a special method was reported by the present inventors in 1980 as “CONFERENCE ON”. METALLIC SCIENCE AND TECHNOLGY
BUDAPEST ”on pages 217-221. Subsequent research has revealed that the same effect can be obtained with the composition disclosed herein, and as a result, the present invention has been achieved. It is considered that the composition fluctuation has already occurred in the quenching state at the stage of forming the amorphous phase, and this fluctuation becomes a site for heterogeneous nucleation, and many uniform and fine nuclei are generated.

The content of Fe in the soft magnetic alloy having the above composition, or the content of each of Fe, Co and Ni, is 80 atomic% or more, and preferably less than 90 atomic%. This is because a high magnetic permeability cannot be obtained if the content exceeds 90 atomic%. However, in order to obtain a saturated magnetic flux density of 1.55 T or more and obtain a high magnetic permeability, 83 to 87% is required.
Atomic% range (below, unless otherwise specified, the numerical range indicated by ８３ includes the upper limit and the lower limit.
Atomic% means 83 atomic% or more and 87 atomic% or less. ), More preferably from 85 to 86
The range of atomic% is more preferable. Unless Fe is contained in an amount of at least 80 atomic%, a desired saturation magnetic flux density cannot be obtained.

Next, Zn in the soft magnetic alloy having the above composition
The content is 0.025 atomic% or more and 0.2
A range of at most atomic% is preferred. If added in this range, the coercive force and iron loss can be reduced and the magnetic permeability can be increased without lowering the high saturation magnetic flux density of 1.5 T or more. Also, regarding the content of Zn,
A range of 0.034 at% or more and 0.160 at% or less is more preferable, and a soft magnetic alloy having lower iron loss, higher saturation magnetic flux density and less change with time can be obtained.

However, since Zn has a melting point of 419.5 ° C. and a boiling point of 908 ° C., when a soft magnetic alloy having the above-described composition is melted in a crucible, the melting temperature is 1240 ° C.
Since the temperature is set at about 1350 ° C., most of the Zn evaporates and disappears. In order to rapidly cool the molten alloy having the above-described composition into an amorphous alloy, the molten metal is sprayed onto a cooling body such as a cooling roll to be rapidly cooled, or an atomizing method of jetting into a cooling gas is performed. In order to allow the quenched alloy to contain the above amount in the above range, it is necessary to add Zn in an amount exceeding the Zn amount as an alloy composition to be put into the crucible.

That is, according to the study of the present inventors, 124
When using a molten metal at a temperature of about 0 to 1350 ° C. to obtain an alloy in the form of a ribbon or powder from the molten metal by a quenching method,
It turned out that it is preferable to set the input amount to about 20 times or more of the target composition. FIG. 4 shows an example of a manufacturing apparatus for obtaining a soft magnetic alloy of the composition of the present invention as a ribbon.
A cooling roll 23 made of copper or steel is rotatably installed inside a chamber 22 which is connected to a vacuum pump 21 via an exhaust pipe 21a and can be evacuated. A crucible 26 having a nozzle 25 made of quartz or the like is provided above the cooling roll 23. A gas supply source 27 is connected to the crucible 26 via a gas supply pipe 27a so that an Ar gas pressure can be applied to the crucible 26. A gas supply source 28 for adjusting the inside of the chamber 22 to a reduced pressure atmosphere of a non-oxidizing gas such as Ar gas is separately connected to the chamber 22 via a gas supply pipe 28a. A lid member is attached to the upper end of the crucible 26, and a gas supply pipe 27 is inserted through the lid member.
The inside of the crucible 26 to which the tip of “a” is connected can be pressurized separately from the internal pressure of the chamber 22.

A heater 29 is provided on the outer periphery of the bottom of the crucible 26.
Is provided so that the molten alloy can be obtained by heating and melting the alloy raw material charged into the crucible 26, and applying the Ar gas pressure from the gas supply source 27 to the inside of the crucible 26. Then, the molten metal is blown out to the surface of the rotating cooling roll 23 through the nozzle 25 to form a thin strip on the side of the cooling roll 23 as indicated by reference numeral 31 in FIG.

Using the manufacturing apparatus shown in FIG.
Was made into an Ar gas atmosphere of about 160 Torr, and (Fe
_0.94-x Zr _0.02 Nb _0.04 B _x ) _100-z Zn _z , x = 0.0
In alloys having the composition of 8, 0.0825, 0.085, Z
When each molten metal having the n amount (z) set to 1, 2, and 3 at% was prepared, and the molten metal was jetted to a rotating cooling roll to produce a ribbon, the Zn of each ribbon sample was produced. The result of analyzing the content is shown in FIG.

As is clear from the results shown in FIG. 5, 0.035 to 0.0575 atomic% of Zn was contained in the ribbon sample obtained from the molten metal obtained by charging 1 atomic% of the Zn raw material into the crucible. 0.07 to 0.125 atomic% Zn remains in the ribbon sample obtained from the melt obtained by charging 2 atomic% Zn into the crucible 1, and 3 atomic% Zn in the crucible 1. 0.12 to 0.170 atomic% of Zn remained in the ribbon sample obtained from the molten metal obtained by charging the sample. In view of the above, in order to include 0.025 to 0.2 atomic% of Zn required in the present invention in the strip sample after quenching, the Zn raw material input amount during the preparation of the molten metal is 0.5 to 4.5. It can be seen that 0 atomic% of Zn is required. Therefore, in the following examples, Zn in the range of 0.025 to 0.2 atomic% is prepared by charging a raw material Zn of about 20 times the target composition into a crucible and manufacturing a ribbon with the apparatus shown in FIG. A soft magnetic alloy sample was prepared.

If the magnetic core shown in FIGS. 1, 2 and 3 is formed by using a ribbon made of a low iron loss Fe-based soft magnetic alloy having a high saturation magnetic flux density manufactured as described above, a high A Fe-based soft magnetic alloy core having both a saturation magnetic flux density and a magnetic permeability, the magnetic permeability is further improved by the effect of adding Zn, the coercive force is low, the breaking strain is large, the bending is strong, and the iron loss is low. be able to.

[0051]

EXAMPLES The soft magnetic alloy ribbon samples shown in the following examples were prepared by a single roll liquid quenching method using the apparatus shown in FIG. That is, a molten metal of a predetermined component is ejected from a nozzle placed on one rotating copper cooling roll onto the cooling roll through a quartz nozzle by the pressure of argon gas, and rapidly cooled to form a ribbon. I got The width of the ribbon prepared as described above was about 15 mm, and the thickness was about 20 μm. The quenched ribbon is made of an alloy mainly composed of amorphous. However, in order to precipitate fine crystal grains of bccFe and improve soft magnetic properties, the annealing treatment is performed after heating to a crystallization temperature or higher and then cooling. Then, a high saturation magnetic flux density low iron loss Fe-based soft magnetic alloy ribbon sample of the present invention and each comparative sample were obtained.

The magnetic permeability of the soft magnetic alloy ribbon sample obtained as described above was determined by processing the ribbon and measuring the outer diameter of 10 mm and the inner diameter of 6 mm.
, And wound around a stacked magnetic core, and measured using an impedance analyzer. The measurement conditions of the magnetic permeability (μ ′) were 5 mOe and 1 kHz. Coercive force (Hc) and magnetic flux density (B ₁₀₎ were measured at 10 Oe by DC B-H loop tracer. Incidentally, B ₁₀ is almost equivalent numbers and saturation magnetic flux density (Bs). FIG.
Among the ribbon samples used in the present invention, (Fe _0.8575 Zr _0.02
The change of structure in the Nb _0.04 B _{0. 0825) 99.88} Zn before and after heat treatment of ribbons _0.12 becomes soft magnetic alloy of the composition in which was examined by X-ray diffraction analysis. From FIG. 6, a broad diffraction pattern peculiar to amorphous is observed in the quenched state (a state in which the molten alloy is rapidly quenched into a thin strip), and after heat treatment, diffraction unique to Fe of body-centered cubic (bcc). The shape is recognized,
It can be seen that the structure of the alloy ribbon used in the present invention was changed from amorphous to body-centered cubic by heat treatment.

FIG. 7 is similar to the composition system used in the present invention.
Fe of composition system_bZr_dNb_eB_xCoercivity of ribbon samples with different compositions
The force measurement results and the alloy ribbon sample of this composition
Zn was added in the range of 0.034 to 0.142 atom%.
Composition system (Fe_{c / 100}Zr_{d / 1 00}Nb_{e / 100}B_{f / 100})
_100-zZn_zOf the coercive force of ribbon samples of different compositions
FIG. In addition, the test to which Zn was added
In the sample shown in FIG._0.855Z
r_0.02Nb_0.04B_0.085)_99.944Zn_0.056Composition test
The sample shown in the_0.855Zr_0.02Nb_0.04B
_0.085)_98.892Zn_0.108The sample with the composition of
(Fe_0.855Zr_0.02Nb_0.04B_0.085)_99.859Zn
_0.141A sample having a composition of_0.8575Zr
_0.02Nb_0.04B_0.0825)_99.96Zn_0.04A sample of the composition of
The sample shown in ()_0.8575Zr_0.02Nb
_0.04B_0.0825)_99.875Zn_{0.12 Five}Sample of composition, shown in
The sample is (Fe_0.8575Zr_0.02Nb_0.04B_0.0825)
_{99.86 7}Zn_0.133A sample having a composition of
_0.86Zr_0.02Nb_0.04B_0.08) _99.966Zn_0.034Composition of
The sample shown in FIG._0.86Zr_0.02Nb_0.04B
_{0 .08})_99.883Zn_0.117The sample with the composition of
(Fe_0.86Zr_0.02Nb_{0. 04}B_0.08)_99.858Zn_0.142
Is a sample having a composition of

In FIG. 7, Zr and Nb are combined at 6 atomic% in total.
In the FeZrNbB-based alloy sample contained, even when B is in the range of 5 to 12.5 at%, it is apparent that by setting the range of 6 to 9.5 at%, a low coercive force of less than 50 mOe is exhibited. And B is within the range of 8 to 9.5 in this range.
Atomic%, Zr is 1.5-2.5 atomic%, Fe + Nb is 89
Particularly low coercivity below 40 mOe in the range of ９０90 at%. In addition, for samples of these compositions,
Samples to which n was added exhibited a low coercive force of less than 100 mOe. In addition, the coercive force is particularly 40 mO.
It has been found that when Zn is added to samples around e and around 50 mOe, the value of the coercive force tends to decrease. In addition, in the sample indicated by the mark “〇” in FIG. 7, when the ribbon sample was obtained by quenching and the ribbon sample was observed with an X-ray, bcc
This is a sample in which diffraction from the (200) peak of bccFe was caused due to precipitation of a part of Fe crystal grains. Further, the sample indicated by ● was a sample in which a diffraction peak from a crystal phase did not appear when X-ray observation was performed in a state where a ribbon was obtained by rapid cooling, which means that the sample was completely amorphous.
Looking at the magnetic properties of each of these samples, the coercive force of the sample that was completely amorphous after quenching was lower.

FIG. 8 is a triangular composition diagram showing the results of measuring the magnetic permeability (μ ′: real part of the complex magnetic permeability) at 1 kHz for the sample described above. In the samples having the composition of the present invention and containing Zn in the range of 0.034 to 0.142 atomic%, all of them show excellent magnetic permeability exceeding 30,000, and Zn in the range of 0.04 to 0.142 atomic%. In the samples added in the range, the magnetic permeability exceeded 40,000.

FIG. 9 is a triangular composition diagram showing a measurement result of a saturation magnetic flux density (B ₁₀ ) obtained from a magnetization curve obtained by applying an applied magnetic field of 10 Oe. It is clear that if the Zr and Nb contents are similar to the composition system of the present invention, a high saturation magnetic flux density exceeding 1.5 T can be obtained. All of the samples to which Zn was added to the alloy samples in the range of 0.034 to 0.142 atomic% showed excellent saturation magnetic flux densities exceeding 1.6 T. Therefore, even if Zn is added within the range of the present invention, the saturation magnetic flux density hardly changes, and it is clear that the value is maintained at a high value.

FIG. 10 shows the first crystallization temperature of the above ribbon sample.
(T_x1Is a crystallization temperature of bccFe).
FIG. 11 shows the intermediate crystallization temperature (T_x1’
FIG. 12 is a triangular composition diagram showing the crystallization temperature of the compound phase).
The second crystallization temperature of the sample (T _x2Is the crystallization temperature of the compound phase
Degree), and FIG. 13 shows T_x2-T_x1Indicated by
ΔT_xFIG.

Hereinafter, the first crystallization temperature, the intermediate crystallization temperature, and the second crystallization temperature will be described. When the temperature of the alloy of the composition system used in the present invention, which is mainly composed of an amorphous phase produced by quenching, is raised, first, bc
An exothermic reaction accompanying the crystallization of the cFe phase occurs, and the crystallization of other compound phases (Fe ₃ B or Fe ₂ B
Exothermic reaction occurs between them, and further exothermic reaction occurs between them depending on the composition. The first exothermic peak is b
This is the largest exothermic peak due to the crystallization of ccFe,
The second exothermic peak corresponds to a first crystallization temperature, the second exothermic peak is a small exothermic peak for forming a compound phase, corresponds to an intermediate crystallization temperature, and the third exothermic peak is a small exothermic peak for forming another compound phase. A peak corresponding to the second crystallization temperature. However, the second exothermic peak may not appear depending on the composition, and the samples with-marks shown in FIG. 11 are samples in which the second exothermic peak does not appear (the intermediate crystallization temperature T _x1 ′ does not appear). Sample). Note that a composition in which the second exothermic peak does not appear has better magnetic characteristics. It can be seen that even if Zn is added to these composition systems, the crystallization temperature hardly changes.

The interval Δ between the crystallization temperatures thus determined
It is preferable that the T _x and 200 ° C. or higher. The ΔT _x shown in FIG. 13 is 200 ° C. or higher, but if it is 200 ° C. or higher, the crystallization temperature interval between the bcc Fe phase and the compound phase is increased. , And only the bccFe phase is precipitated to suppress the precipitation of other compounds, and it is easy to improve the soft magnetic properties. Therefore, the heat treatment temperature of the alloy is preferably performed between the first crystallization temperature and the second crystallization temperature (the temperature between T _x1 and T _x2 ).

FIG. 14 shows a composition system similar to the composition of the present invention.
FIG. 4 is a triangular composition diagram showing the crystal grain size of a ribbon sample of a composition system not containing n. The test results described below show that the addition of Zn in the composition range of the present invention to this composition system slightly reduces the crystal grain size. Therefore, the present inventors have confirmed. Therefore, it can be seen that even in the alloy of the composition system of the present invention, crystal grains having a particle diameter of 12 nm or less, preferably 11 nm or less can be obtained. FIG. 15 is a triangular composition diagram showing the magnetostriction (λs) of a ribbon sample of a composition system similar to the composition of the present invention but not containing Zn. Even if Zn is added to this composition system, the magnetostriction is the same. The present inventors have confirmed that this is the case. Therefore, it can be seen that even in the alloy of the present invention in which Zn is added to the alloy of the composition shown in FIG.

FIG. 16 shows the dependency of the crystal grain size (D) on the Zn concentration in the alloy ribbon sample of the present invention to which Zn is added. There was a tendency for the crystal grain size to slightly decrease due to the effect of Zn addition. FIG. 17 shows the Zn concentration dependence of the magnetostriction (λs) of the alloy ribbon sample of the present invention to which Zn is added. There is a clear tendency for magnetostriction to decrease due to the Zn addition effect, but the amount of change is slight.

FIG. 18 shows that an alloy sample having a composition of Fe _85.75 Zr ₂ Nb ₄ B _8.25 contains Zn at 0.12 atomic% or 0.13 atomic%.
The iron loss of a magnetic core sample using a low iron loss Fe-based soft magnetic alloy ribbon to which atomic% was added was measured by an AC magnetometer, and the results are shown for the ribbon sample having the composition of Fe ₇₈ Si ₉ B ₁₃ of the comparative example. The comparison is shown. As is clear from the results shown in FIG. 18, the iron loss of the ribbon sample of the present invention is smaller than that of the sample of the comparative example. The ribbon sample of the present invention has a core loss of 0.1 W / k at 1.4T.
g of the silicon steel sheet.
It is clear that the excellent value of about / 10, which is a fraction of that of the Fe-based amorphous.

FIG.₇₈Si₉B₁₃Comparison of different compositions
Example sample and Fe₈₅Zr_1.75Nb_4.25B₉Comparison of different compositions
Example sample and Fe_85.5Zr_TwoNb_FourB_8.5Comparative example of different compositions
Sample and Fe_85.75Zr_2.25Nb_3.75B_8.25Of composition
Comparative sample and (Fe_0.8575Zr_0.02Nb
_0.04B_0.0825)_99.88Zn_0.12Alloy of the present invention having a different composition
Temporal change of iron loss of magnetic core obtained from core sample (at 200 ° C
After heating for a fixed time, the temperature was returned to normal temperature and measured). In FIG.
As is evident from the results shown, the magnetic core sample of the present invention has Fe Fe
₇₈Si ₉B₁₃Much smaller than the comparative sample
Excellent characteristics that hardly change over time while maintaining the same iron loss
Commanded. In addition, almost the same composition without adding Zn
Compared with the comparative sample, the iron loss is lower and the rate of change is lower.
It is clear. The core sample in this example has iron loss.
Excellent value of less than 0.1w / kg even after heating for 500 hours
Is shown.

Tables 1 and 2 show the elapsed time dependence of the iron loss, coercive force, and magnetic permeability of each sample used in FIG. Table 1
As is clear from the results shown in Table 2 and Table 2, even in the core sample according to the present invention to which Zn was added, the core sample in which the ratio of Zr and Nb was set to a particularly preferable range (see Table 1 (F
e _0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _Core loss value itself (0.081 to _0.0 ) of _99.88 Zn _0.12 composition magnetic core sample).
90), the rate of change is small, and the coercive force is also small (0.
038) and excellent magnetic permeability (60200-6120)
0) is clear.

[0065]

[Table 1]

[0066]

[Table 2]

FIG. 20 shows a magnetic core sample made of a soft magnetic alloy ribbon having the same composition as the magnetic core sample used in FIG.
FIG. 21 shows iron loss measurement results at room temperature after heating for a predetermined time.
Indicates the time change rate of the iron loss shown in FIG. FIG. 20 and FIG.
From the results shown in FIG. 1, the magnetic core sample of the present invention shows that Fe ₇₈ Si ₉ B
₁₃ shows a much smaller iron loss change rate than the core sample of the comparative example having a composition of ₁₃ and does not contain Zn-containing Fe _85.75 Zr _2.25 Nb.
_{It was found that the} sample had a lower iron loss change rate than the comparative sample having the composition of _3.75 B _8.25 . from these things,
It has been found that by adding a small amount of Zn to the FeNbZrB-based alloy within the range specified in the present invention, the iron loss can be further reduced, and the rate of change with time of the iron loss can be reduced.

FIG. 22 shows a thin ribbon sample having a thickness of 20 μm, which is a comparative sample having a composition of Fe ₇₈ Si ₉ B ₁₃ and a comparative sample having a composition of Fe ₈₄ Zr _3.5 Nb _3.5 B ₈ Cu _1. , Fe ₉₀ Zr ₇ B ₃ and Fe ₈₄
A comparative sample having a composition of Nb ₇ B ₉ and Fe _73.5 Si _13.5 B
A comparative sample having a composition of ₉ Nb ₃ Cu ₁ and Fe _85.5 Zr ₂ N
A comparative sample having a composition of b ₄ B ₈ and (Fe _0.855 Zr _0.02
For the alloy sample of the present invention having the composition of Nb _0.04 B _0.085 ) _99.86 Zn _0.14 , the bending diameter (Df: mm: to what extent the bending radius could be processed without breaking) and the fracture strain (λf: 10 ⁻³⁾ : Strain at break).

In the bending deformation in this case, two rods and a ribbon sample are used, a ribbon arranged between the two rods is sandwiched, and the two rods are gradually approached to form a peak. When the ribbon is bent and cut in this manner, the distance between the end faces of the rod when the ribbon is broken and cut is L, and when the thickness of the ribbon is t, t / (L-
The value of t) was defined as breaking strain (λf). The result is shown in FIG. The samples of the present invention having the compositions shown in FIG. 22 to FIG. 22 were able to reduce the bending diameter and obtain a material that was not easily broken at an appropriate heat treatment temperature of 510 to 520 ° C. Note that the heat treatment temperature is different as shown in FIG. 22 because the crystallization temperature is different in each composition system. However, the heating rate during the heat treatment is 180 ° C./min for each sample. And then cooling after holding at the heat treatment temperature of 5 minutes. The fact that these fracture bending characteristics are excellent is effective when winding a ribbon of soft magnetic alloy into a transformer to prevent cracks from forming in the ribbon. In the case of processing the core, it means that the core is not easily broken, so that the yield can be improved and the number of steps can be reduced. Particularly, in the case of an alloy of the composition system of the present invention, in which a predetermined amount of Zn is added and the ratio of Zr and Nb is in a preferable range, the heat treatment is performed at 510 ° C. and 520 ° C. Since the bend can be bent to a diameter of 2 mm or less, it is clear that the workability after heat treatment of the core wound with the ribbon is improved.

FIG. 23 shows (Fe _0.86 Nb _0.07 B _0.07 )
The Zn coercivity of the soft magnetic alloy ribbon having the composition of _100-z Zn _z shows dependency on the Zn concentration, but it is clear that the coercive force tends to be reduced by the addition of Zn.
The coercive force reaches a minimum level in the range of 04 to 0.07 at%, and the coercive force gradually increases with an increase in the Zn concentration. It showed low coercive force. FIG. 24 shows the Zn concentration dependence of the magnetic permeability of the soft magnetic alloy ribbon sample of the same composition. The magnetic permeability was improved by adding Zn,
The maximum was shown at 7 atomic%, and it was found that the magnetic permeability gradually decreased thereafter. Therefore, even if the alloy has a composition that could not be used conventionally, by adding Zn,
It becomes a practical soft magnetic alloy, and the practically usable composition range of the Fe-MB soft magnetic alloy increases.

FIG. 25 shows that (Fe _0.86 Zr _0.02 Nb _0.04 B
_0.08 ) The dependency of the coercive force of the soft magnetic alloy ribbon having the composition of _100-z Zn _z on the Zn concentration is shown. As with the test results of the alloy ribbon shown in FIG. The sample having 0.133 atomic% Zn added had a lower value of about 65% as compared with the sample without Zn addition, indicating that the coercive force can be reduced by adding Zn. FIG. 26 shows the Zn concentration dependence of the magnetic permeability of the soft magnetic alloy ribbon sample of the same composition. The magnetic permeability was improved by adding Zn, and 0.133 atomic%.
It was clarified that the magnetic permeability showed the maximum value by adding. The test results of the coercive force and the magnetic permeability shown in FIGS. 25 and 26 are superior to the test results shown in FIGS. 23 and 24 because the content ratios of Zr and Nb of the samples used in each test are determined by the soft magnetic characteristics. Is more preferable (1.5 /
This is because 6 ≦ Zr / (Zr + Nb) ≦ 2.5 / 6).

Next, Table 3 shows FeNbB-based alloy samples and FeZ
rB-based alloy sample, FeHfB-based alloy sample and FeZrNb
The values of magnetic permeability (μ ′: 1 kHz), coercive force (Hc: Oe), and saturation magnetic flux density (B ₁₀ : T) when a predetermined amount of Zn is added to the B-based alloy sample are described. Table 3 also shows samples to which Zn was not added.

[0073]

[Table 3]

In Table 3, the FeNbB-based sample No. 16 was obtained by adding 0.07 atomic% of Zn, and the FeZrB-based sample No. 17 was obtained by adding 0.1 atomic% of Zn. The sample added was No. 11 and F
An eHfB-based sample of No. 18 was prepared by adding 0.1 atomic% of Zn to the sample of No. 12, and a sample of No. 19 was obtained by adding 0.13 atomic% of Zn to a sample of No. 13 similarly. The sample of No. 20 was obtained by adding 0.13 atomic% of Zn to the sample of No. 20, and the sample of No. 14 was obtained by adding 0.14 atomic% of Zn to the sample of No. 21. It is a sample of.

From the results shown in Table 3, it can be seen that in any of the composition systems, the addition of Zn significantly improves the magnetic permeability.
It became clear that the coercive force was reduced and the saturation magnetic flux density exhibited an excellent value of about 1.6T. Therefore, it is clear that by using a Zn-added alloy in the composition system of the alloy used in the present invention, the saturation magnetic flux density can be maintained in a high range of about 1.6 T and the magnetic permeability can be improved. An excellent magnetic core can be obtained by forming the magnetic core using an alloy having this composition. In the composition system of the alloy used in the present invention, particularly, in the case where Nb and Zr are used as the element M, and the ratio of Zr and Nb is in a preferable range, and a specified amount of Zn is added, In particular, it shows high permeability and low coercive force, and at the same time, 1.6
Since an alloy capable of obtaining an excellent saturation magnetic flux density exceeding T can be obtained, a magnetic core having excellent characteristics can be obtained by using this alloy.

[0076]

As described above, according to the present invention, F
e as a main component, Ti, Zr, Hf, V, Nb,
It contains at least one of Ta, Mo, and W, and further contains B and Zn, and at least 50% or more of the structure has an average crystal grain size of 100% or more.
Since it is composed of fine crystal grains of bccFe of nm or less and the remainder is composed of an amorphous alloy, it has both high saturation magnetic flux density and magnetic permeability, and the magnetic permeability is further improved by the effect of adding Zn, and the coercive force is low, Since a fracture strain is large, and a high saturation magnetic flux density and low iron loss Fe-based soft magnetic alloy that is strong against bending can be provided, by forming a magnetic core from this soft magnetic alloy,
High permeability, high saturation magnetic flux density, low coercive force,
A magnetic core with small iron loss can be obtained. More specifically, in the present invention, the rate of change of iron loss by heating at 320 ° C. for 100 hours is 20% or less, the saturation magnetic flux density is 1.5 T or more, and the magnetic permeability is 30 by adjusting the content of the component elements.
A magnetic core having excellent characteristics of 000 or more can be obtained.

Next, the present invention relates to the composition formula (Fe _1-a Q _a ) _b
The B _x M _y Zn _z, or composition formula Fe _{b B x} M _y
Depending on Zn _z or the composition formula (Fe _1-a Q _a ) _b B
The _{x M y Zn z M 'u} , or composition formula Fe _b B _x
M _y Zn _z is represented by, Q is Co, is at least one of Ni, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
W is at least one kind, and M ′ is at least one kind selected from Cr, Ru, Rh, and Ir. A ≦ 0.05, 80 atom% ≦ b, 5 atom% ≦ x ≦ 12. 5 atomic%, 5 atomic% ≦ y ≦
If 7.5 atomic% and 0.025 atomic% ≦ z ≦ 0.2 atomic%, high saturation magnetic flux density and magnetic permeability can be obtained at the same time, and the magnetic permeability is further improved by the effect of adding Zn. It is possible to provide a magnetic core made of a high saturation magnetic flux density and low iron loss Fe-based soft magnetic alloy that has a low magnetic force, a large fracture strain, and a high bending resistance.

More specifically, by adjusting the content of the element M in the above composition range, the rate of change of iron loss by heating at 200 ° C. for 500 hours is 10% or less, the saturation magnetic flux density is 1.5 T or more, and the frequency is 50 Hz. A high saturation magnetic flux density and low iron loss Fe-based soft magnetic alloy having excellent characteristics with an iron loss of 0.15 kg / W or less when a magnetic flux of 1.4 T is applied can be reliably obtained. The high saturation magnetic flux density and low iron loss Fe
If the magnetic core is made of a soft magnetic alloy, one
Since a fracture strain of 0 × 10 ⁻³ or more can be obtained and a material that is strong against bending can be obtained, a magnetic core made of an alloy having excellent workability and having no defects such as strain and cracks can be obtained.

In the above composition ratio, Zr and Nb are selected as the element M, the total amount of Zr and Nb is adjusted to 5.0 to 7.5 atomic%, and Zr with respect to the total amount of Zr and Nb is adjusted.
In the case where the ratio of the amount of r is adjusted to a range of 1.5 / 6 to 2.5 / 6 and Zn is added in a specified amount, particularly excellent saturation magnetic flux density and magnetic permeability are shown. A magnetic core showing particularly low iron loss can be obtained.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view showing a first embodiment of a magnetic core according to the present invention.

FIG. 2 is an exploded perspective view showing a second embodiment of the magnetic core according to the present invention.

FIG. 3 is a perspective view showing a third embodiment of the magnetic core according to the present invention.

FIG. 4 is a sectional view showing a part of an example of an apparatus for producing a soft magnetic alloy used for producing a magnetic core of the present invention.

FIG. 5 is a diagram showing the relationship between the amount of Zn put into a crucible used for producing a soft magnetic alloy used for the magnetic core of the present invention and the Zn analysis value of the obtained alloy ribbon sample.

FIG. 6 shows (Fe) of an alloy used for the magnetic core of the present invention.
It is an X-ray diffraction _pattern before and after heat treatment of a sample having a composition of _0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.88 Zn _0.12 .

Figure 7 is a result of the coercive force of the alloy samples of Fe _b Zr _d Nb _{e B x} having a composition of composition system similar to the alloy used in the present invention the magnetic core was measured, the alloy of this composition system 0 .03
Triangular composition diagram showing a _{4~0.142 (Fe b Zr d Nb e} B x) of the composition system with the addition of Zn in atomic percent ranges result of _100-z Zn _z becomes the coercive force of the alloy samples of the composition were measured is there.

FIG. 8 is a triangular composition diagram showing the results of measuring the magnetic permeability (μ ′: real part of the magnetic permeability) at 1 kHz for an alloy sample having the same composition as the alloy sample whose test results are shown in FIG. is there.

9 is a saturation magnetic flux density (B ₁₀ ) obtained from a magnetization curve obtained by applying an applied magnetic field of 10 Oe to an alloy sample having the same composition as the alloy sample whose test results are shown in FIG.
FIG.

FIG. 10 is a triangular composition diagram showing the first crystallization temperature (T _x1 is the crystallization temperature of bccFe) of the above alloy sample.

FIG. 11 is a triangular composition diagram showing the intermediate crystallization temperature (T _x1 ′ is the crystallization temperature of the compound phase) of the above alloy sample.

FIG. 12 is a triangular composition diagram showing a second crystallization temperature (T _x2 is a crystallization temperature of a compound phase) of the above alloy sample.

FIG. 13 is a graph _showing T _x2 −T
FIG. 3 is a triangular composition diagram showing ΔT _x indicated by _x1 .

FIG. 14 is a triangular composition diagram showing the crystal grain size of an alloy sample of a composition system similar to the alloy used for the magnetic core of the present invention and containing no Zn.

FIG. 15 shows the magnetostriction (λ) of an alloy sample having a composition similar to the alloy used for the magnetic core of the present invention and containing no Zn.
It is a triangle composition figure showing s).

FIG. 16 is a diagram showing the Zn concentration dependency of the crystal grain size (D) of the alloy sample according to the present invention to which Zn is added.

FIG. 17 is a diagram showing the Zn concentration dependency of magnetostriction (λs) of an alloy sample according to the present invention to which Zn is added.

FIG. 16 is an AC magnetization characteristic measuring apparatus for iron loss of a magnetic core sample made of an alloy having a composition of Fe _85.75 Zr ₂ Nb ₄ B _8.25 to which Zn is added at 0.12 atomic% or 0.13 atomic%. The result measured by the method of Comparative Example F
FIG. 8 is a diagram showing a comparison with numerical values of a thin magnetic core sample having a composition of e ₇₈ Si ₉ B ₁₃ .

Figure 19 is a comparative example core samples Fe ₇₈ Si ₉ B ₁₃ having a composition, in the comparative example core samples _{Fe 8 5.75 Zr 2.25 Nb 3.75 B} 8.25 a composition, (Fe _0.8575 Zr _{0. 02} Nb
FIG. 9 is a graph showing the time-dependent change in iron loss (measured at room temperature after heating at 200 ° C.) of the alloy core sample of the present invention having a composition of _0.04 B _0.0825 ) _99.88 Zn _0.12 .

FIG. 20 is a diagram showing the iron loss of a core sample at room temperature after heating at 320 ° C. for a predetermined time using a sample having the same composition as the sample used in FIG. 19;

FIG. 21 is a diagram showing a time change rate of the iron loss shown in FIG. 20;

FIG. 22 is a diagram showing the values of bending diameter and fracture strain of alloy ribbon samples having a plate thickness of 20 μm, each of which is a comparative alloy sample having various compositions and an alloy sample having the composition of the present invention. is there.

FIG. 23 is a diagram showing the Zn concentration dependence of the coercive force of a FeNbB-based alloy sample.

FIG. 24 is a diagram showing the Zn concentration dependence of the magnetic permeability of a FeNbB-based alloy sample.

FIG. 25 is a diagram showing the Zn concentration dependence of the coercive force of a FeZrNbB-based alloy sample.

FIG. 26 is a diagram showing the Zn concentration dependence of the magnetic permeability of a FeZrNbB-based alloy sample.

[Explanation of symbols]

1 ... vacuum pump, 2 ... chamber, 3 ... cooling roll,
5 Nozzle, 6 Crucible, 27, 28 Gas supply source, 29 Heater, 10 Melt.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiro Makino 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Akinobu Kojima 1-7 Yukitani-Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Yutaka Yamamoto 1-7 Yukitani Otsuka-cho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Akihisa Inoue 35 Motokawa, Kawauchi, Aoba-ku, Sendai, Miyagi Housing 11-806 (72) Inventor Takeshi Masumoto 3-8-22 Uesugi, Aoba-ku, Sendai-shi, Miyagi F-term (reference) 4E004 DB02 NA05 NB07 NC04 TA01 TA03 TB04 5E041 AA11 AA19 CA02 HB11 NN01 NN06 NN13 NN15 NN17

Claims (14)

[Claims] 1. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. _{(Fe 1-a Q a)} b B x M y Zn z where, Q is Co, a or Ni,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and a, b, x, y, and z indicating the composition ratio are a ≦ 0.05, 80 atom% ≦ b, 5 atom% ≦ x ≦ 12.5 atom%, 5 atom% ≦ y ≦ 7.5 atom%, 0.025 atom% ≦
z ≦ 0.2 atomic%. 2. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. Fe _{b B x} M _y Zn _z where, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W
B, x, y, and z indicating the composition ratio are as follows: 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%. 3. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. (Fe _1-a Q _a ) _b B _x M _y Zn _z M ′ _u where Q is one or both of Co and Ni;
In Ti, Zr, Hf, V, Nb, Ta, Mo, W
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, and a, b indicating a composition ratio , X,
y, z and u are a ≦ 0.05, 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦
z ≦ 0.2 at% and u ≦ 5 at%. 4. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. _{Fe b B x M y Zn z} M 'u wherein M is, Ti, Zr, Hf, V , Nb, Ta, Mo,
One or more elements selected from W
M ′ is one or more elements selected from Cr, Ru, Rh and Ir, and b, x, y,
z and u are 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%, u ≦ 5 atomic%. 5. The method according to claim 1, further comprising Fe, Zr, Nb and B.
n, at least 50% or more of the structure is made of fine crystal grains of bccFe having an average crystal grain size of 100 nm or less, and the remainder is made of a low iron loss Fe-based soft magnetic alloy made of an amorphous alloy. A low iron loss Fe-based soft magnetic alloy core. 6. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. _{(Fe 1-a Q a)} b Zr c Nb d B x Zn z where, Q is Co, a or Ni,
The composition ratios a, b, c, d, x, and z are as follows: a ≦ 0.05, 80 at% ≦ b, 1.5 at% ≦ c ≦ 2.5.
Atomic%, 3.5 atomic% ≦ d ≦ 5.0 atomic%, 5 atomic% ≦ x
≦ 12.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%
And 5.0 atomic% ≦ c + d ≦ 7.5 atomic%, 1.5 /
6 ≦ c / (c + d) ≦ 2.5 / 6. 7. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. _{Fe b Zr c Nb d B x} Zn z However, b showing the composition ratio, c, d, x, z is 80 atomic%
≦ b, 1.5 atomic% ≦ c ≦ 2.5 atomic%, 3.5 atomic% ≦ d
≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.0
25 atomic% ≦ z ≦ 0.2 atomic%, and 5.0 atomic% ≦ c
+ D ≦ 7.5 atomic%, 1.5 / 6 ≦ c / (c + d) ≦ 2.
5/6. 8. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. . _{(Fe 1-a Q a)} b Zr c Nb d B x Zn z M 'u where Q is Co, a or Ni,
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, and a, b, c,
d, x, z, and u are a ≦ 0.05, 80 atomic% ≦ b, 1.5 atomic% ≦ c ≦ 2.5
Atomic%, 3.5 atomic% ≦ d ≦ 5.0 atomic%, 5 atomic% ≦ x
≦ 12.5 at%, 0.025 at% ≦ z ≦ 0.2 at%, u ≦ 5 at%, 5.0 at% ≦ c + d ≦ 7.5
Atomic%, 1.5 / 6 ≦ c / (c + d) ≦ 2.5 / 6. 9. A bc having a composition represented by the following formula, wherein at least 50% or more of the structure has an average crystal grain size of 100 nm or less.
consisting of fine grains of cFe, the remainder consisting of an amorphous alloy phase, the fine grains of bccFe quenching the alloy,
It is made of a low iron loss Fe-based soft magnetic alloy characterized in that the amorphous phase is a single phase structure, and then the amorphous phase is heated and cooled to a crystallization temperature or higher and then cooled and precipitated. A low iron loss Fe-based soft magnetic alloy magnetic core. _{Fe b Zr c Nb d B x} Zn z M 'u where M' is, Cr, Ru, Rh, is one or more elements selected from among Ir, b showing the composition ratio, c,
d, x, z, and u are 80 atomic% ≦ b, 1.5 atomic% ≦ c ≦ 2.5 atomic%, 3.5
Atomic% ≦ d ≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.025 atomic% ≦ z ≦ 0.2 atomic%, u ≦ 5 atomic%
And 5.0 atomic% ≦ c + d ≦ 7.5 atomic%, 1.5 /
6 ≦ c / (c + d) ≦ 2.5 / 6. 10. The low iron loss Fe-based soft magnetic alloy core according to claim 1, wherein the temperature is 200 ° C.
The rate of change of iron loss by heating for 500 hours is 10% or less, the saturation magnetic flux density is 1.5T or more, and the iron loss when applying a magnetic flux of 1.4T at a frequency of 50Hz is 0.15W / kg or less. A low iron loss Fe-based soft magnetic alloy core. 11. The low iron loss F according to claim 6, wherein:
In the e-based soft magnetic alloy core, b, c,
d and x are 83 atomic% ≦ b, 5.7 ≦ c + d ≦ 6.5 atomic%, 1.5 / 6 ≦ c / (c + d) /≦2.5/6, 6 atomic% ≦ x ≦ 9.5 Atomic%, low iron loss F
e-based soft magnetic alloy core. 12. The low iron loss Fe-based soft magnetic alloy has a fracture strain of 1
The low iron loss Fe-based soft magnetic alloy core according to claim 1, wherein the core is 0 × 10 ⁻³ or more. 13. The method according to claim 1, wherein one or two or more annular bodies formed from the low iron loss Fe-based soft magnetic ribbon are laminated. Low iron loss Fe-based soft magnetic alloy core. 14. The low iron loss Fe according to claim 1, comprising a ring formed by winding a ribbon of the low iron loss Fe-based soft magnetic alloy into an annular shape. Soft magnetic alloy core.