JP2001279404A - Soft magnetic alloy with fine crystal structure and is producing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft magnetic alloy with a fine crystal structure having high magnetic permeability, also exhibiting low coercive force and more improved in soft magnetic properties and to provide its producing method. SOLUTION: This soft magnetic alloy with a fine crystal structure is obtained by rapid cooling from the molten alloy, by which the multiple phase is formed composed of an amorphous phase and a Fe and B compound phase or composed of an amorphous phase, a Fe and B compound phase of and a bcc-Fe phase (mainly of the crystal grains of Fe with a body-centered cubic structure). The rapid cooled alloy is subjected to a heat treatment to precipitate the fine crystal grains of a bcc-Fe phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft magnetic alloy having a fine crystal structure used for a magnetic head, a transformer, a choke coil and the like, and a method for producing the same. In particular, the present invention relates to a high magnetic permeability and low coercive force. The present invention relates to a soft magnetic alloy having a certain fine crystal structure and a method for producing the same.

[0002]

2. Description of the Related Art The characteristics generally required of a soft magnetic alloy used for a magnetic head, a transformer, a choke coil and the like are as follows. High saturation magnetic flux density. High permeability. Low coercive force. Therefore, when manufacturing a soft magnetic alloy or a magnetic head,
From these viewpoints, materials have been studied in various alloy systems. Conventionally, Sendust,
Crystalline alloys such as permalloy and silicon steel are used, and recently, Fe-based and Co-based amorphous alloys have been used.

[0003] However, although Sendust is excellent in soft magnetic properties, it has a drawback that the saturation magnetic flux density is as low as about 1.1 T (tesla), and Permalloy also has an alloy composition excellent in soft magnetic properties. The saturation magnetic flux density is approx.
It has a drawback as low as 8T, and silicon steel has a drawback in that although the saturation magnetic flux density is high, the soft magnetic properties 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. As described above, it is difficult to combine high saturation magnetic flux density with excellent soft magnetic characteristics.

The important characteristics of a soft magnetic alloy for transformers are low iron loss and high saturation magnetic flux density. However, Fe-based alloys for transformers conventionally used for some applications have been used. Since the amorphous alloy has a saturation magnetic flux density of 1.56 T, there has been a demand to further increase the saturation magnetic flux density.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present inventors
Amorphous alloy phase and bcc-
An Fe-based soft magnetic alloy having a structure mainly composed of Fe phase fine crystal grains, having a saturation magnetic flux density exceeding 1.5 T and a magnetic permeability exceeding 10,000 is provided. One of the Fe-based soft magnetic alloys was a high saturation magnetic flux density alloy having a composition represented by the following formula. (Fe _1-m Q _m ) _n 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 contains one or both of Zr and Hf; ≦ 0.0
5, n ≦ 93 at%, x = 5.0 to 8 at%, y = 4 to 9
Atomic%. Another one of the Fe-based soft magnetic alloys is
The high saturation magnetic flux density alloy was characterized by having a composition represented by the following formula. Fe _k B _x M _1y where k ≦ 93 at%, x = 5.0 to 8 at%, y = 4 to
9 atomic%.

Further, as a method for producing these Fe-based soft magnetic alloys, an amorphous alloy ribbon obtained by rapid cooling by spraying a molten alloy onto a cooling body rotating at a high speed is subjected to a heat treatment. At the time of quenching, fine crystal grains of the bcc-Fe phase are generated in an alloy ribbon composed of an amorphous phase, and a soft magnetic alloy exhibiting excellent soft magnetic properties has been obtained.

However, in recent years, in the case of a magnetic head, a more suitable magnetic material for a high-performance magnetic head has been developed in order to cope with a higher coercive force of the magnetic recording medium accompanying a higher recording density of the magnetic recording medium. Wanted and also a transformer,
In the case of choke coils, further downsizing is required in accordance with the downsizing of electronic devices. Therefore, higher performance magnetic materials are desired. There is a demand for a soft magnetic alloy having a higher magnetic permeability and a lower coercive force than a magnetic alloy.

The present invention has been made to solve the above-mentioned problems, and has a high magnetic permeability and a low coercive force.
An object of the present invention is to provide a soft magnetic alloy having a fine crystal structure with further improved soft magnetic properties and a method for producing the same.

[0009]

In order to achieve the above object, the present invention employs the following constitution. The soft magnetic alloy having a fine crystalline structure according to the present invention has an amorphous phase and a compound phase of Fe and B, or an amorphous phase, a compound phase of Fe and B and a bcc-Fe phase after quenching the alloy melt. An alloy having a multiphase structure composed of (mainly Fe crystal grains having a body-centered cubic structure) is subjected to heat treatment to precipitate fine bcc-Fe phase crystal grains. In the soft magnetic alloy having such a fine crystal structure, the alloy structure after quenching the molten alloy is such that a compound phase of Fe and B or a compound phase of Fe and B and a bcc-Fe phase are precipitated in addition to the amorphous phase. It can have a multiphase structure, and the compound of Fe and B is bcc-
In order to promote the generation of Fe crystal nuclei and to refine the bcc-Fe crystal grains, the crystal deposition temperature is lowered.
The number of fine bcc-Fe crystal grains precipitated by heat treatment is increased, and high magnetic permeability and low coercive force can be obtained.
Soft magnetic characteristics can be improved.

Further, the soft magnetic alloy having a fine crystal structure of the present invention having the above-described structure is preferably represented by the following composition formula. _{T 100-abc M a X b} Nb c where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
X represents at least one element among W, Cr, X represents one or more elements containing at least B among B, P, and C, and a, b, and c indicating composition ratios are atomic%; 0 ≦ a ≦
3, 2 ≦ b ≦ 18 and 4 ≦ c ≦ 8.

Further, the soft magnetic alloy having a fine crystal structure of the present invention having the above-mentioned structure is preferably represented by the following composition formula. _{T 100-abcde M a X b} Nb c M 'd Z e where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
W represents at least one element of Cr, X represents one or more elements containing at least B of B, P, and C, and M ′ represents one of Pt, Au, Pd, Ag, and Cu. Z represents Zr, Ti, H
a, b, c, d, and e, which represent at least one of f, Al, Y, and rare earth elements, and indicate the composition ratio, are atomic%, and 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, 4 ≦ c ≦ 8, 0 <
d ≦ 3 and 0 ≦ e ≦ 3. As the rare earth element,
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
b, Dy, Ho, Er, Tm, Yb, and Lu are selected and used, and among them, Nd, La, and Ce are particularly preferable. Further, a misch metal made of an inexpensive rare earth element is also preferable.

It is preferable that the soft magnetic alloy having the fine crystal structure of the present invention having the above-mentioned structure is represented by the following composition formula. T _100-abcef M _a X _b N _{b c} Z _e G a _f where T represents one or more elements including at least Fe among Fe, Co, and Ni, and M represents V, Mn, Mo, Ta,
X represents at least one element among W, Cr, X represents one or more elements containing at least B among B, P, and C, and Z represents Zr, Ti, Hf, Al, Y, and a rare earth element. A, b, c, e, and f, which represent at least one element among the above, and indicate the composition ratio, are atomic%, and 0 ≦ a ≦ 3, 2 ≦
b ≦ 18, 4 ≦ c ≦ 8, 0 ≦ e ≦ 3, and 0 <f ≦ 3.

Further, the soft magnetic alloy having a fine crystal structure of the present invention having the above-mentioned structure is preferably represented by the following composition formula. _{T 100-abcdef M a X b} Nb c M 'd Z e Ga f where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
W represents at least one element of Cr, X represents one or more elements containing at least B of B, P, and C, and M ′ represents one of Pt, Au, Pd, Ag, and Cu. Z represents Zr, Ti, H
a, b, c, d, e, f representing at least one of f, Al, Y and rare earth elements
Is atomic%, 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, 4 ≦ c ≦ 8,
0 <d ≦ 3, 0 ≦ e ≦ 3, and 0 <f ≦ 3.

Further, it is represented by any one of the above formulas.
In the soft magnetic alloy having a fine crystal structure of the present invention,
In the above composition formulas, a, b, and c indicating the composition ratios are represented by atomic%, and are 0.1%.
1 ≦ a ≦ 1, 8 ≦ b ≦ 13, and 5 ≦ c ≦ 7.
Is more preferable. In addition, the above T_100-abcdeM_aX_bNb_c
M '_dZ_e Or T_100-abcdefM_aX_bNb_cM '_dZ
_eGa_f In the composition formula, d indicating the composition ratio is atomic%, and 0
It is more preferable that <d ≦ 0.1. Also, the above
T_100-abcdeM_aX_bNb_cM '_dZ_e Or T
_100-abcefM _aX_bNb_cZ_eGa_fOr T
_100-abcdefM_aX_bNb_cM '_dZ_eGa_f Composition formula
In the formula, e indicating the composition ratio is atomic%, and 0 <e ≦ 2.
Is more preferred. In addition, the above T_100-abcefM_aX_b
Nb_cZ_eGa_fOr T_100-abcdefM_aX_bNb
_cM '_dZ_eGa_f In the formula, f indicating the composition ratio is an atom
%, It is more preferable that 0 <f ≦ 1.

Further, the soft magnetic alloy having a fine crystal structure of the present invention having any one of the above structures can exhibit an effective magnetic permeability at 1 kHz of 33,000 or more.

Further, the method for producing a soft magnetic alloy having a fine crystal structure according to the present invention is characterized in that the molten alloy is rapidly cooled to form an amorphous phase and a compound phase of Fe and B or an amorphous phase and a compound phase of Fe and B. After forming an alloy having a multi-phase structure composed of a phase and a bcc-Fe phase, the alloy is subjected to a heat treatment to precipitate fine bcc-Fe phase crystal grains. Such a method for producing a soft magnetic alloy having a fine crystal structure of the present invention is suitably used for producing a soft magnetic alloy having a fine crystal structure of the present invention.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a soft magnetic alloy having a fine crystal structure and a method for producing the same according to the present invention will be described. First, the soft magnetic alloy having a fine crystal structure of the present invention will be described. The soft magnetic alloy having a fine crystalline structure according to the present invention has an amorphous phase and an F phase after quenching the molten alloy.
Heat treatment is applied to an alloy having a dual phase structure composed of a compound phase of e and B or an amorphous phase, a compound phase of Fe and B, and a bcc-Fe phase to precipitate fine bcc-Fe phase crystal grains. It is made to let. The composition shown below is
It is a composition formula based on an analysis value.

The soft magnetic alloy having a fine crystal structure of the present invention can be represented by the following composition formula. _{T 100-abc M a X b} Nb c where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
X represents at least one element among W, Cr, X represents one or more elements containing at least B among B, P, and C, and a, b, and c indicating composition ratios are atomic% (at %)
Where 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, and 4 ≦ c ≦ 8.

Further, the soft magnet having the fine crystal structure of the present invention
The conductive alloy has the above-mentioned T_100-abcM_aX _bNb_cComposition
In order to improve the ability to form an amorphous phase in a molten gold, Pt, A
element of at least one of u, Pd, Ag, and Cu
Element M ', Zr, Ti, Hf, Al, Y and rare earth elements
The following group to which at least one or more elements Z are added
It may be represented by a formula. T_100-abcdeM_aX_bNb_cM '_dZ_e However, T contains at least Fe among Fe, Co, and Ni.
M represents V, Mn, Mo, Ta,
X represents at least one element of W and Cr, and X is
At least one element containing at least B among B, P and C
M ′ represents Pt, Au, Pd, Ag, or Cu
Z represents Zr, Ti, H
at least one of f, Al, Y and rare earth elements
A, b, c, d, and e, which represent the above elements and indicate the composition ratio, are
0% ≦ a ≦ 3, 2 ≦ b ≦ 18, 4 ≦ c
≦ 8, 0 <d ≦ 3, 0 ≦ e ≦ 3.

Further, the soft magnet having the fine crystal structure of the present invention
The conductive alloy has the above-mentioned T_100-abcM_aX _bNb_cComposition
In order to improve the ability to form an amorphous phase, Zr, T
i, Hf, Al, Y and at least one of the rare earth elements
Bcc containing at least one element Z and containing Fe as a main component
To refine the crystal grain size of the phase (body-centered cubic phase)
It may be represented by the following composition formula to which Ga is added.
No. T_100-abcefM_aX_bNb_cZ_eGa_f However, T contains at least Fe among Fe, Co, and Ni.
M represents V, Mn, Mo, Ta,
X represents at least one element of W and Cr, and X is
At least one element containing at least B among B, P and C
And Z is Zr, Ti, Hf, Al, Y and a rare earth element
Represents at least one element of the elements
A, b, c, e, and f shown are atomic% (at%) and 0 ≦ a
≦ 3, 2 ≦ b ≦ 18, 4 ≦ c ≦ 8, 0 ≦ e ≦ 3, 0 <f
≦ 3.

Further, the soft magnet having the fine crystal structure of the present invention
The conductive alloy has the above-mentioned T_100-abcM_aX _bNb_cComposition
Pt, A to improve the ability to form amorphous
element of at least one of u, Pd, Ag, and Cu
Element M ', Zr, Ti, Hf, Al, Y and rare earth elements
Adding at least one element Z among
-Addition of Ga to reduce the grain size of Fe phase
Alternatively, it may be represented by the following composition formula. T_100-abcdefM_aX_bNb_cM '_dZ_eGa_f However, T contains at least Fe among Fe, Co, and Ni.
M represents V, Mn, Mo, Ta,
X represents at least one element of W and Cr, and X is
At least one element containing at least B among B, P and C
M ′ represents Pt, Au, Pd, Ag, or Cu
Z represents Zr, Ti, H
at least one of f, Al, Y and rare earth elements
A, b, c, d, e, f representing the above elements and indicating the composition ratio
Is atomic% (at%), 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, 4
≦ c ≦ 8, 0 <d ≦ 3, 0 ≦ e ≦ 3, 0 <f ≦ 3
You.

The present invention represented by any one of the above formulas
Soft magnetic alloy having a fine crystal structure of
In the formula, a, b, and c indicating the composition ratio are atomic%, and 0.1 ≦ a
≦ 1, 8 ≦ b ≦ 13, and 5 ≦ c ≦ 7 are more preferable.
New In addition, the above T_100-abcdeM_aX_bNb_cM '_d
Z_e Or T_100-abcdefM_aX_bNb_cM '_dZ_eGa
_f In the composition formula, d indicating the composition ratio is atomic%, and 0 <d
It is more preferred that ≦ 0.1. In addition, the above T
_100-abcdeM_aX_bNb_cM '_dZ_e Or T
_100-abcefM _aX_bNb_cZ_eGa_fOr T
_100-abcdefM_aX_bNb_cM '_dZ_eGa_f Composition formula
In the formula, e indicating the composition ratio is atomic%, and 0 <e ≦ 2.
Is more preferred. In addition, the above T_100-abcefM_aX_b
Nb_cZ_eGa_fOr T_100-abcdefM_aX_bNb
_cM '_dZ_eGa_f In the formula, f indicating the composition ratio is an atom
%, It is more preferable that 0 <f ≦ 1.

The soft magnetic alloy having a fine crystal structure of the present invention has an average crystal grain size of 100 nm or less, preferably 30 nm.
m, which is mainly composed of a microcrystalline phase consisting of a fine bcc-Fe phase of m or less, and has a structure composed of the microcrystalline phase and a grain boundary amorphous phase present at the grain boundaries, and has a high saturation magnetic flux. In addition to showing density and excellent magnetic permeability, it shows low coercive force. It is because the alloy structure after quenching the molten alloy has a compound phase of Fe and B or a compound phase of Fe and B in addition to the amorphous phase and bc.
It has a dual phase structure in which a c-Fe phase is precipitated.
And the compound of B promote the generation of bcc-Fe crystal nuclei and reduce the crystal precipitation temperature in order to refine the bcc-Fe crystal grains.
The crystal grains of cc-Fe increase, and the precipitated bcc
It is considered that the crystal magnetic anisotropy is averaged due to the magnetic interaction between the crystal grains of the bcc structure and the apparent crystal magnetic anisotropy is reduced because the crystal grains of -Fe are as fine as 100 nm or less. Can be

Further, the soft magnetic alloy of the present invention comprises an amorphous phase and a compound phase of Fe and B or an amorphous phase, a compound phase of Fe and B and a bcc-Fe phase by rapidly cooling the molten alloy. After forming an alloy having a multi-phase structure, the alloy is heat-treated to precipitate fine bcc-Fe phase crystal grains, so that the effective magnetic permeability at 1 kHz is 10,000 or more. Value can be shown.

In the soft magnetic alloy of the present invention having the above composition system, the main components, Fe, Co, and Ni, are elements that contribute to magnetism and are important for obtaining a high saturation magnetic flux density and excellent soft magnetic properties. is there. In the alloy having the composition of T _100-abc M _a X _b Nb _{c, the value of 100-abc} indicating the addition amount (composition ratio) of the element T responsible for magnetism is 71 to 94 atomic%. In addition, when the element M ′ or the element Z is included, the value of 100-a-b-c-d-e indicating the amount of addition (composition ratio) of the element T responsible for magnetism is 65 atomic% to 94 atomic%.
In the case where the content is smaller than the atomic% and the element Z or the element Ga is contained, the addition amount (composition ratio) of the element T which contributes to magnetism is 10
The value of 0-abc-ef is 65 atomic% or more and less than 94 atomic%, and the above-mentioned element M ′, element Z, and element Ga
Is included, the value of 100-abcdcef indicating the amount of addition (composition ratio) of the element T responsible for magnetism is at least 62 atomic% and less than 94 atomic%. When the addition amount of the element T bearing the above magnetism exceeds 94 atomic%, when the molten alloy is quenched by a liquid quenching method such as a single roll method, the alloy structure after quenching has a favorable amorphous phase. Is difficult, and as a result, the structure of the soft magnetic alloy obtained after the heat treatment is not uniform, so that high magnetic permeability cannot be obtained, which is not preferable.

In order to obtain a saturation magnetic flux density (Bs) of 1.5 T or more, the addition amount of the element T is preferably set to 75 atomic% or more. Composition ratio) is set to 75 atomic% or more and 94 atomic%.

A part of Fe may be replaced by one or more elements of Co and Ni in order to adjust magnetostriction and the like. In this case, the content of Fe is preferably 25% or less of Fe. Is good. Outside this range, the magnetic permeability deteriorates. It is preferable to select at least Fe as the element T in the above composition formula, since it can reduce the cost and increase the saturation magnetic flux density.

B among the elements X in the above composition formula includes a compound having an effect of increasing the amorphous forming ability of the soft magnetic alloy, an effect of preventing the crystal structure from being coarsened, and a compound having a bad influence on the magnetic properties in the heat treatment step. It is considered that there is an effect of suppressing generation of a phase. Further, P and C in the element X have an affinity with Zr, Ti, and Hf in Nb and the element Z, particularly,
Since it has a strong affinity with Zr, bcc containing Fe as the main component
Phase does not form a solid solution in the phase (body-centered cubic phase) but remains in the amorphous phase.
In the same way as above, the decrease in saturation magnetic flux density can be reduced,
In addition, the specific resistance can be increased, and soft magnetic characteristics such as magnetic permeability can be improved. P and C are inexpensive. By adding these P and / or C, even if the addition amount of B, Nb or the element Z is reduced, the saturation magnetic flux density and the magnetostriction are not deteriorated, and the permeability and the like can be reduced. Since the soft magnetic characteristics can be improved, the cost can be reduced. It is preferable to include B as the element X as an essential element in that the soft magnetic characteristics can be improved.

If b, which indicates the added amount of the element X, is less than 2 atomic%, the amorphous phase at the grain boundary becomes unstable, so that a sufficient effect of addition cannot be obtained. When b exceeds 18 atomic%,
After heat treatment, B-Nb-based, BM (Zr, Ti, H
In the f) system and the Fe-B system, the tendency of boride formation is increased, the heat treatment conditions for obtaining a fine crystal structure are restricted, and good soft magnetic properties cannot be obtained. By adjusting the addition amount of the element X in this manner, the average crystal grain size of the fine crystal phase to be precipitated is 100 nm or less, preferably 30 nm or less.
nm or less. Therefore, the above element X
Is 2 atomic% or more and 18 atomic% or less. In addition, it is preferable that b indicating the amount of addition of the element X be 8 atom% or more and 13 atoms or less. If b, which indicates the amount of the element X added, exceeds 13 atomic%, the saturation magnetic flux density is undesirably reduced. When b is less than 8 atomic%,
A relatively coarse crystal phase is present in the alloy after quenching, and it is not preferable because it is difficult to obtain a fine structure after heat treatment of this alloy.

Nb in the above composition formula is considered to hardly form a solid solution with α-Fe. However, by rapidly cooling the molten alloy so that the structure of the alloy has an amorphous phase,
Has a function of improving the soft magnetic properties of the obtained soft magnetic alloy by forming a solid solution in a supersaturated state, adjusting a solid solution amount of Nb by a heat treatment performed thereafter, partially crystallizing and precipitating as a fine crystalline phase. . Further, in order to precipitate a fine crystal phase and to suppress the coarsening of the crystal grains of the fine crystal phase, it is considered that it is necessary to leave an amorphous phase which may be an obstacle to crystal grain growth at the grain boundary. . Further, the grain boundary amorphous phase is a solid solution of Nb discharged from α-Fe due to an increase in heat treatment temperature, thereby deteriorating soft magnetic characteristics.
It is considered that the formation of the b-based compound is suppressed. Therefore, F
It is preferable to add B as the element X to the e-Nb alloy. Further, in the soft magnetic alloy of the present invention, in order to easily obtain an amorphous phase without oxidizing the material, it is preferable to include Nb which is hardly oxidized and has a particularly high amorphous forming ability. preferable. Nb is a relatively slow diffusion species, and the addition of Nb is considered to have the effect of reducing the growth rate of fine crystal nuclei and the ability to form an amorphous phase, and is effective in making the structure finer. In addition, Nb has a small absolute value of free energy for forming oxides, is thermally stable, and hardly generates oxides. Therefore, Nb is effective as a material for preventing oxidization of a material when rapidly cooling a molten alloy. .

If c, which represents the amount of Nb added, is less than 4 atomic%, the effect of reducing the nucleus growth rate is reduced, and the crystal grain size becomes coarse, resulting in a decrease in soft magnetism. If c, which indicates the amount of Nb added, exceeds 8 atomic%, Nb-B or Fe-Nb
The tendency of formation of the system compound increases, and the characteristics are deteriorated. Therefore, the addition amount of Nb is 4 atom% or more and 8% or more.
It is preferably at most atomic%. In addition, c indicating the amount of Nb added is set to 5 atom% or more and 7 atom% or less.
It is preferable because the magnetic properties of the obtained soft magnetic alloy having a fine crystal structure can be set in the most preferable range.

Further, the soft magnetic alloy of the present invention has the effect of reducing the growth rate of fine crystal nuclei, the ability to form an amorphous phase, and the elements M that are not easily oxidized.
One or more of Ta, W, and Cr may be added. Among these, Mo is particularly small in absolute value of free energy of formation of oxide, is thermally stable, and is hard to form oxide. A indicating the amount of element M added
Is from 0 atomic% to 3 atomic%, preferably from 0 atomic% to 1 atomic%. A indicating the addition amount of the element M is 3
If the content exceeds the atomic%, the amorphous phase of the alloy structure immediately after quenching the molten alloy can be uniform, and the soft magnetism of the obtained soft magnetic alloy will be low. Further, a indicating the addition amount of the element M is set to be 0.1 atomic% or more and 1 atomic% or less in that the amorphous phase in the structure of the alloy immediately after quenching the molten alloy tends to be uniform. preferable.

In the soft magnetic alloy of the present invention, Zr, Ti, H
At least one or more of f, Al, Y and rare earth elements may be added. The rare earth elements here include La, Ce, Pr, Nd, Pm, Sm, E
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)
It is used by selecting from among them. Z of the above elements Z
r and Hf have particularly high amorphous forming ability, and a part of Zr and Hf can be replaced with Ti. Z of the above elements Z
Although it is said that r and Hf hardly form a solid solution with α-Fe, Zr and Hf are super-saturated by rapidly cooling the molten alloy so that the structure of the alloy has an amorphous phase. The subsequent heat treatment adjusts the solid solution amount of these elements to partially crystallize and precipitate as a fine crystalline phase, thereby improving the soft magnetic properties of the obtained soft magnetic alloy. Further, in order to precipitate a fine crystal phase and to suppress the coarsening of the crystal grains of the fine crystal phase, it is considered that it is necessary to leave an amorphous phase which may be an obstacle to crystal grain growth at the grain boundary. . Further, this grain boundary amorphous phase is formed by Zr and Hf discharged from α-Fe due to an increase in the heat treatment temperature.
Dissolves the element M such as
It is considered that the formation of the eZ-based compound is suppressed. Also,
Among Zr and Hf, Hf is a very expensive element, and therefore, it is more preferable to include Zr in consideration of the raw material cost. Such an element Z is a relatively slow diffusing species,
The addition of the element Z is considered to have the effect of reducing the growth rate of the fine crystal nuclei and the ability to form an amorphous phase, and is effective in miniaturizing the structure.

Of the above-mentioned element Z, Al is known as a metalloid element, and a body-centered cubic phase (b
(cc-Fe phase). Al has the effect of increasing the electrical resistance of the soft magnetic alloy and reducing iron loss, but Al has a particularly large effect. Among the above elements Z, Y, rare earth elements (La, Ce, Pr, Nd, Pm, S
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
Lu) is an element having an ability to form an amorphous phase, and the type of the selected element can control the volume fraction of the amorphous phase in the soft magnetic alloy by adjusting the amount of addition. The reason is that Y and the rare earth element are bc mainly composed of Fe.
It does not dissolve in c phase (body-centered cubic phase) but remains in the amorphous phase,
Further, by changing the element used, the magnetostriction can be controlled and the magnetic characteristics can be improved.

If e, which indicates the addition amount of the element Z, exceeds 3 atomic%, these elements are easily oxidized, so that the material is easily oxidized when the molten alloy is rapidly cooled, and the structure of the alloy after the rapid cooling is changed. It becomes difficult to uniformly form the amorphous phase. When at least one of Y and rare earth elements is added as the element Z, the value e indicating the addition amount of the element Z is set to 2 atomic% or less. Can be improved and the coercive force reduced,
This is preferable in that the soft magnetic characteristics can be improved and the amount of the expensive element M, Nb or B added can be reduced. Also,
In particular, when a rare earth element is added as the element Z to the soft magnetic alloy of the present invention, the alloy structure after quenching the alloy melt easily precipitates a compound phase of Fe and B in addition to the amorphous phase. Since the compound of Fe and B promotes the generation of bcc-Fe crystal nuclei and refines the crystal grains of bcc-Fe, the crystal precipitation temperature is lowered. Fe crystal grains are increased, high magnetic permeability and low coercive force can be obtained, and soft magnetic characteristics can be improved.

The soft magnetic alloy of the present invention contains Cu, A
g, Au, Pd, Pt
When the content is at most atomic%, preferably at most 2 atomic%, the soft magnetic properties are improved. By adding a small amount of an element that does not form a solid solution with Fe, such as Cu, the composition fluctuates and C
u forms a cluster at an early stage of crystallization, and a relatively Fe-rich region is generated, so that the frequency of α-Fe nucleation can be increased. Further, when the crystallization temperature was measured by differential thermal analysis, it seems that the addition of the above-mentioned elements such as Cu and Ag slightly lowers the crystallization temperature. This is considered to be due to the fact that the addition makes the amorphous non-uniform, and as a result, the stability of the amorphous is reduced. When a non-uniform amorphous phase is crystallized, a large number of regions are likely to be partially crystallized, and non-uniform nuclei are generated. Therefore, the obtained composition is considered to have a fine grain structure. From the above viewpoints, similar effects can be expected for elements other than these elements that lower the crystallization temperature.

In the soft magnetic alloy of the present invention, Ga
The content is preferably at most atomic%, more preferably at most 1 atomic%. Ga is known as a metalloid element, and Ga forms a solid solution in a bcc phase (body-centered cubic phase) containing Fe as a main component. If the content of Ga exceeds 3 atomic%, it is not preferable because the magnetostriction increases, the saturation magnetic flux density decreases, or the magnetic permeability decreases. Ga has the effect of increasing the electrical resistance of the soft magnetic alloy and reducing iron loss.
Ga also has the effect of reducing the crystal grain size. Therefore, the effect of adding Ga is particularly large.

In addition, other than the above elements, if necessary, Zn,
Si, Cd, In, Sn, Pb, As, Sb, Bi, S
By adding elements such as e, Te, Li, Be, Mg, Ca, Sr, and Ba, the magnetostriction of the soft magnetic alloy can be adjusted. In addition, in the soft magnetic alloy of the above composition system,
Of course, unavoidable impurities such as H, N, O, and S can be regarded as having the same composition as the soft magnetic alloy used in the present invention even if they are contained to such an extent that desired characteristics are not deteriorated. .

In the soft magnetic alloy having a fine crystal structure according to the present invention, the alloy structure after quenching the molten alloy has a compound phase of Fe and B or a compound phase of Fe and B in addition to the amorphous phase.
A c-Fe phase can be formed into a multi-phase structure, and the compound of Fe and B promotes the generation of bcc-Fe crystal nuclei, and in order to refine bcc-Fe crystal grains,
Since the crystal precipitation temperature is lowered, the number of fine bcc-Fe crystal grains precipitated by the heat treatment increases, the magnetic permeability can be increased, the coercive force can be reduced, and excellent soft magnetic characteristics can be obtained.

In order to produce a soft magnetic alloy having a fine crystalline structure of the present invention as described above, for example, T
_{100-abcde M a X b Nb} c M 'd Z e, or T
_100-abcef M _a X _b N _{b c} Z _e G a _f or T
_{100-abcdef M a X b Nb} c M 'd Z e Ga f based amorphous alloy or crystalline alloy containing an amorphous phase (where, T 1 or containing the Fe, Co, at least Fe of Ni M represents at least one element among V, Mn, Mo, Ta, W, and Cr, and X represents B, P, C
Represents at least one element containing at least B,
M ′ represents at least one element of Pt, Au, Pd, Ag, and Cu, and Z represents Zr, Ti, Hf, A
l, Y, and at least one of the rare earth elements) are quenched by a fluid cooling method, a quenching method using a single roll, or the like, and the alloy melt is melted by arc melting, high frequency induction melting, or the like. At this time, by controlling the liquid quenching condition, the alloy structure after quenching the molten alloy is changed to a compound phase of Fe and B or Fe and B in addition to the amorphous phase.
Of the compound phase and the bcc-Fe phase.

Then, the alloy ribbon having the above-mentioned double-phase structure is subjected to a heat treatment, whereby an amorphous phase and an average grain size of 100 n are obtained.
A structure mixed with a fine crystal phase consisting of crystal grains of a bcc-Fe phase of m or less is obtained, and a desired Fe-based soft magnetic alloy is obtained. The heat treatment resulted in the precipitation of a fine crystal structure composed of fine Fe crystal grains having an average crystal grain size of 100 nm or less and having a bcc structure.
It has a double phase structure composed of a compound phase of e and B or an amorphous phase, a compound phase of Fe and B, and a bcc-Fe phase (mainly crystal grains of Fe having a body-centered cubic structure). The compound of B promotes the generation of bcc-Fe crystal nuclei,
Since the crystal precipitation temperature is lowered in order to make the crystal grains of bcc-Fe fine, many fine bcc-Fe crystal grains can be precipitated at a certain temperature or higher.

The temperature at which the fine crystalline phase composed of bcc-Fe is deposited depends on the composition of the alloy.
K) to about 550 ° C. (823 K). Also this bc
At a temperature higher than the temperature at which the fine crystalline phase of c-Fe is precipitated, a compound phase that deteriorates the soft magnetic properties such as Fe ₃ B or Fe ₃ Zr when the alloy contains Zr is deposited after the heat treatment. . Therefore, in the present invention,
The holding temperature at the time of heat treatment of the alloy ribbon having the above-mentioned dual phase structure is in the range of 500 ° C. (773 K) to 700 ° C. (973 K), and the fine crystalline phase mainly composed of Fe crystal grains having a body-centered cubic structure. Is preferably set according to the composition of the alloy so that a compound phase such as Fe ₃ Zr, which deteriorates soft magnetic properties, does not precipitate.

The heating rate when the temperature is raised to the above heat treatment temperature is preferably in the range of 10 to 180 ° C./min (10 to 180 K / min), and is preferably in the range of 40 to 180 ° C./min (40 to 180 K
/ Min) is more preferable. Further, the time for holding the alloy ribbon composed of the above-mentioned double-phase structure at the above-mentioned holding temperature can be 5 to 60 minutes. As a result, the desired effect can be obtained. Further, if the holding time is longer than 60 minutes, the magnetic properties are not improved, and the manufacturing time is prolonged and productivity is deteriorated, which is not preferable.

[0044]

The present invention will be described more specifically with reference to the following examples. Experimental Example 1 to adjust the material to be _{Fe 84 Nb 7-e B 9} Nd e a composition (Preparation 1 of the alloy ribbon) (e = 0 to 0.4 atomic%), it N ₂ gas High frequency melting was performed in an atmosphere, and the melted raw material was poured into a mold to obtain a mother alloy. Next, in a N ₂ gas atmosphere, the above-mentioned mother alloy is melted at a high frequency in a melt nozzle of an alloy ribbon manufacturing apparatus, and the obtained alloy melt is injected onto a cooling surface of a copper roll rotating at a high speed from a tip of a molten metal blowing part. When the alloy quenching was performed by the liquid quenching method of quenching, various alloy ribbons were obtained by changing to the following liquid quenching conditions 1 and 2. The composition of these alloy ribbons is Fe ₈₄ Nb _6.85 B
₉ Nd was _0.15 . In addition, Nd (trace element) in the ribbon
Are those analyzed by energy dispersive spectroscopy (EDS). Hereinafter, the amount of Nd in the composition of the ribbon is a result of analysis by EDS.

Here, the liquid quenching condition 1 is as follows.
Injection of gap width 0.2mm at the tip of molten metal outlet
Temperature 1190 ° C (1463K), Injection pressure 39200P
a (0.4 kgf / cm^Two), Back pressure -53200Pa
(-40cmHg), copper roll outer diameter 20cm, roll times
The number of turns is 3600 rpm and the roll peripheral speed is 37.7 m / s.
You. The liquid quenching condition 2 is based on the molten metal nozzle
0.25 mm gap width at the end, injection temperature 1350 ° C
(1623K), injection pressure 83300Pa (0.85k)
gf / cm^Two), Back pressure -79800Pa (-60cmH
g), copper roll outer diameter 60cm, roll rotation speed 1400r
pm and a roll peripheral speed of 44.0 m / s.
Next, the various alloy ribbons obtained were heated at a rate of 180 ° C /
Min (180 K / min), heat treatment temperature 650 ° C. (923
K), the heat treatment was performed at the heat treatment temperature for 5 minutes.
Various alloy ribbons with a thickness of 20 μm and a width of 15 mm
Was. What was obtained under the liquid quenching condition 1 was the alloy thin film of Example 1.
The band obtained in the liquid quenching condition 2 was the band of Comparative Example 1.
It is an alloy ribbon. The composition of these ribbon alloys is Fe
₈₄Nb_6.85B ₉Nd_0.15Met.

(Physical Properties of Alloy Strip) FIG.
Fe immediately after quenching obtained under quenching conditions₈₄Nb_6.85B₉Nd_0
.15-Rays of alloy ribbons of the following composition (alloy ribbon before heat treatment)
4 shows the results of diffraction measurement. As is clear from FIG.
The alloy ribbon of Comparative Example 1 manufactured under the cold condition 2 was characterized by being amorphous.
Has a halo diffraction pattern and body-centered cubic Fe as the main component
Of the (110) plane of the bcc phase (bcc-Fe)
And (200) plane peak,
It was found that the bcc-Fe phase was precipitated in the material phase.
Call On the other hand, Example 1 manufactured under liquid quenching condition 1
The alloy ribbon of halo has a halo diffraction pattern unique to amorphous and F
A unique diffraction pattern is observed in the compound phase of e and B.
Is there a slight diffraction pattern unique to body-centered cubic crystals?
In the amorphous phase, Fe _ThreeCrystal of B or Fe_3.5B result
And bcc-Fe phase precipitated slightly.
You can see that From these facts, the alloy ribbon immediately after quenching
Liquid quenching conditions differ even if the composition is the same
It can be seen that the crystals precipitated in the amorphous phase are different.

(Magnetic Properties of Alloy Strip) Next, the coercive force (Hc) and the effective magnetic permeability (μ) at 1 kHz of the alloy ribbons of Example 1 and Comparative Example 1 (alloy ribbon after heat treatment) were measured. The results are shown in FIG. From the results shown in FIG. 1, it is understood that the alloy ribbon of Example 1 has a higher effective magnetic permeability and a lower coercive force than the alloy ribbon of Comparative Example 1. From this, the alloy ribbon of Example 1 in which the alloy ribbon of the dual phase structure in which the crystal of the compound of Fe and B such as Fe ₃ B or Fe _3.5 B was precipitated in the amorphous phase by quenching was heat-treated, F after quenching
It can be seen that soft magnetic properties are superior to the alloy ribbon of Comparative Example 1 in which the alloy ribbon in which the crystal of the compound of e and B is not precipitated in the amorphous phase is heat-treated.

[0048] [Experimental Example 2] to adjust the material to be _{Fe 84 Nb 7-e B 9} Nd e a composition (Preparation 2 of the alloy ribbon) (e = 0~0.4at%),
It was melted by high frequency in an N ₂ gas atmosphere, and the melted raw material was poured into a mold to obtain a mother alloy. Next, in a N ₂ gas atmosphere, the above-mentioned mother alloy is melted at a high frequency in a melt nozzle of an alloy ribbon manufacturing apparatus, and the obtained alloy melt is injected onto a cooling surface of a copper roll rotating at a high speed from a tip of a molten metal blowing part. When manufacturing alloy ribbons by the liquid quenching method,
Various alloy ribbon samples were obtained by changing the liquid quenching conditions 3 to 5 below. The composition of these alloy ribbon samples was Fe ₈₄ Nb _6.92.
B ₉ Nd was _0.08 .

Here, the liquid quenching condition 3 is as follows: a gap width of 0.2 mm at the tip of the molten metal blowing part of the molten metal nozzle, an injection temperature of 1190 ° C. (1463 K), and an injection pressure of 39200 P
a (0.4 kgf / cm ² ), back pressure -53200 Pa
(-40 cmHg), a copper roll outer diameter of 20 cm, a roll rotation speed of 3600 rpm, and a roll peripheral speed of 37.7 m / s. The liquid quenching condition 4 is as follows: a gap width of 0.25 mm at the tip of the molten metal blowing portion of the molten metal nozzle, an injection temperature of 1375 ° C. (1468 K), and an injection pressure of 83300 Pa
(0.85 kgf / cm ² ), back pressure -79800 Pa
(−60 cmHg), a copper roll outer diameter of 60 cm, a roll rotation speed of 1400 rpm, and a roll peripheral speed of 44.0 m / s. The liquid quenching condition 5 is as follows: a gap width of 0.25 mm at the tip of the molten metal blowing portion of the molten metal nozzle, an injection temperature of 1350 ° C. (1623 K), and an injection pressure of 83300 Pa.
(0.85 kgf / cm ² ), back pressure -79800 Pa
(−60 cmHg), a copper roll outer diameter of 60 cm, a roll rotation speed of 1400 rpm, and a roll peripheral speed of 44.0 m / s.

Next, the various alloy ribbons thus obtained were heated at a heating rate of 180 ° C./min (180 K / min), a heat treatment temperature of 650 ° C. (923 K), and a holding time at this heat treatment temperature of 5 minutes. Was performed to obtain various alloy ribbons having a thickness of 20 μm and a width of 15 mm. Example 2 obtained under liquid quenching condition 3 was
The alloy ribbon obtained under the liquid quenching condition 4 is the alloy ribbon of Comparative Example 2, and the alloy ribbon obtained under the liquid quenching condition is the alloy ribbon of Comparative Example 3. The composition of these alloy ribbons was Fe ₈₄ Nb _6.92 B ₉ Nd _0.08 .

(Physical Properties of Alloy Strip) FIG.
Fe immediately after quenching obtained under quenching conditions₈₄Nb_6.92B₉Nd_0
.08-Rays of alloy ribbons of the following composition (alloy ribbon before heat treatment)
4 shows the results of diffraction measurement. As is clear from FIG.
The alloy ribbons of Comparative Examples 2 and 3 manufactured under the cold conditions 4 and 5 were non-rolled.
Halo diffraction pattern peculiar to crystal quality and body-centered cubic Fe
(110) plane of bcc phase (bcc-Fe) as the main component
Peak of (200) plane and peak of (200)
Are bcc-Fe phases precipitated in the amorphous phase.
You can see that. On the other hand, it was manufactured under liquid quenching condition 3.
The alloy ribbon of Example 2 has a halo diffraction pattern unique to amorphous.
Unique diffraction pattern was observed in shape and compound phase of Fe and B
And a slight diffraction pattern unique to the body-centered cubic crystal was observed.
Therefore, Fe in the amorphous phase _ThreeCrystal of B or F
e_3.5It can be seen that the crystals of B precipitated. This
From these facts, the alloy ribbon immediately after quenching has the same composition.
However, if the liquid quenching conditions are different,
It can be seen that the emitted crystals are different.

(Magnetic Properties of Alloy Strip) Next, the coercive force (Hc) and the effective magnetic permeability (μ) at 1 kHz of the alloy ribbons of Example 2 and Comparative Examples 2 and 3 (alloy ribbons after heat treatment). Are shown in FIG. From the results shown in FIG. 2, it can be seen that the alloy ribbon of Example 2 has a higher effective magnetic permeability and a lower coercive force than the alloy ribbons of Comparative Examples 2 and 3. From this, quenching caused Fe ₃ B or Fe in the amorphous phase.
_3.5 The alloy ribbon of Example 2 in which the alloy ribbon of the dual phase structure in which the crystal of the compound of Fe and B is precipitated as in B is heat-treated, the crystal of the compound of Fe and B is in the amorphous phase after quenching. It can be seen that the soft magnetic properties are superior to those of the alloy ribbons of Comparative Examples 2 and 3 in which the alloy ribbon that has not been precipitated is heat-treated. Also, it can be seen that the alloy ribbon of Example 2 can increase the effective magnetic permeability at 1 kHz and lower the coercive force than the alloy ribbon of Example 1 by increasing the amount of Nd added.

[Experimental Example 3] (Preparation of Alloy Strip 3) Fe₈₄Nb_6.9R_0.1B₉(R =
Y, La, Ce, Nd, Sm, Gd, Dy)
(Feed) or Fe prepared to be
₈₄Nb_6.8R_0.2B ₉(R = La, Ce, Pr, Nd, S
m, Gd) are prepared as N_TwoMoth
Melted in a hot air atmosphere and pour the melted raw material into the mold
A mother alloy was obtained. Then N_TwoIn a gas atmosphere,
High frequency melting of the above master alloy in the melt nozzle of the gold ribbon manufacturing equipment
From the tip of the molten metal blow-out section.
Injects onto the cooling surface of the copper roll rotating at high speed to quench
When manufacturing alloy ribbons by the liquid quenching method,
In the case of Examples 3 to 14,
Alloy ribbon (Fe₈₄Nb_6.9R_0.1B₉(R = Y, La, C
e, Nd, Sm, Gd, Dy), Fe₈₄Nb
_6.8R_0.2B₉(R = La, Ce, Pr, Nd, Gd)
Obtained. These alloy thins were analyzed by EDS.
Not described, but in terms of input composition. Here, various
When quenching the molten alloy, blow out the molten metal from the molten metal nozzle.
Gap width at the tip of the part 0.2 mm, injection pressure 3920
0 Pa (0.4 kgf / cm^Two), Back pressure -53200P
a (-40 cmHg), and the outer diameter of the copper roll is 20
cm.

[0054]

[Table 1]

[0055]

[Table 2]

In Table 2, amor. Represents an amorphous phase, b
cc (200) indicates the (200) plane of the bcc-Fe phase. Next, the obtained various alloy ribbons were heated at a heating rate of 180 ° C./min (180 K / min.) Up to the heat treatment temperature Ta shown in Table 2.
Min), and heat treatment was performed for 5 minutes at the heat treatment temperature Ta to obtain various alloy ribbons (Examples 3 to 14) having a thickness of 20 μm and a width of 15 mm.

For comparison, the same procedure as in Example 3 was carried out except that a raw material prepared to have a composition of Fe ₈₄ Nb ₇ B ₉ was used.
An alloy ribbon was obtained under the same liquid quenching conditions as in Example 1 and the heat treatment temperature Ta
At a heating rate of 180 ° C./min (180 K / min) up to 675 ° C. (948 K), and a holding time of 5 at the heat treatment temperature Ta.
Then, an alloy ribbon (composition of Fe ₈₄ Nb ₇ B ₉ ) of Comparative Example 4 having a thickness of 20 μm and a width of 15 mm was obtained.

(Physical Properties of Alloy Strip) FIG. 3 shows Fe ₈₄ Nb _6.9 R _0.1 B ₉ immediately after quenching obtained under the above-mentioned liquid quenching conditions.
(R = Y, La, Ce, Nd, Sm) alloy ribbon (alloy ribbon before heat treatment), Fe ₈₄ Nb _6.8 R _0.2 B
₉ shows the results of X-ray diffraction measurement of an alloy ribbon having a composition of ₉ (R = Pr) (alloy ribbon before heat treatment) and an alloy ribbon having a composition of Fe ₈₄ Nb ₇ B ₉ (before heat treatment). Table 2 shows that Fe
The alloy ribbon of Comparative Example 4 having a composition of ₈₄ Nb ₇ B ₉ and Fe ₈₄
Compositions of alloy ribbons of Examples 3 to 14 in which Y or a rare earth element (La, Ce, Pr, Nd, Sm, Gd, Dy) was added to an alloy having a composition of Nb ₇ B ₉ by Nb substitution, and immediately after quenching. The result of having investigated the structure of the alloy ribbon by X-ray diffraction is shown.

As is clear from FIG. 3, the alloy ribbon immediately after quenching in Comparative Example 4 having the composition of Fe ₈₄ Nb ₇ B ₉ has a halo diffraction pattern peculiar to the amorphous phase and a body-centered cubic Fe. The peak of the (200) plane of the bcc phase (bcc-Fe) as the main component is recognized, indicating that the bcc-Fe phase was precipitated in the amorphous phase. On the other hand, Fe ₈₄
Alloy ribbons of Examples 3, 4, 6, 8, 9, 10 immediately after quenching, in which Y or a rare earth element (La, Ce, Pr, Nd, Sm) was added to an alloy having a composition of Nb ₇ B ₉ by Nb substitution. Indicates a halo diffraction pattern unique to amorphous and a diffraction pattern unique to the compound phase of Fe and B (peak shape formed from 47.5 ° to around 57.5 is asymmetric). It can be seen that Fe ₃ B crystals or Fe _3.5 B crystals were precipitated in the solid phase. Further, in the alloy ribbon immediately after quenching in Example 10, a slight diffraction pattern unique to body-centered cubic crystal was observed, and bcc-crystal other than Fe ₃ B crystal or Fe _3.5 B crystal was contained in the amorphous phase. It can be seen that the Fe phase is also precipitated.
Furthermore, alloy ribbon after quenching of Comparative Example 4 as apparent Fe ₈₄ Nb ₇ B ₉ having a composition of Table 2, but is not observed the precipitation of crystals of Fe ₃ B, consisting Fe ₈₄ Nb ₇ B ₉ Nb-substituted Y or rare earth elements (La, Ce, P
(r, Nd, Sm) in each of the alloy strips immediately after quenching in Examples 3 to 14 in which precipitation of Fe ₃ B crystals was observed, and a double phase structure of an amorphous phase and Fe ₃ B crystals was observed. It can be seen that it is composed of From these facts, Fe-Nb-
It can be seen that, in a molten alloy obtained by adding Y or a rare earth element to a B-based alloy by Nb substitution, crystals of Fe ₃ B are easily precipitated by rapid cooling.

(Magnetic Properties of Alloy Strip)
Alloy ribbon after heat treatment of 4, 6, 8, 9, 10 and Comparative Example 4
Coercive force (Hc) of alloy ribbon after heat treatment
Fig. 3 shows the results of measuring the effective magnetic permeability (μ)
Show. Further, the alloy ribbon after heat treatment of Examples 3 to 14,
The coercive force (Hc) of the alloy ribbon after heat treatment of Comparative Example 4 was 1 k
The result of measuring the effective magnetic permeability (μ) at _Ten
Table 2 shows the results of measuring the residual magnetic flux density Br
You. B here_TenIs the mark of 10 Oe (800 A / m)
This is the magnetic flux density in an applied magnetic field.

From the results shown in FIG. 3 and Table 2, it can be seen that the effective magnetic permeability of the alloy ribbon of Comparative Example 4 was 34,600 and the coercive force was 6.4 A / m. In contrast, the alloy ribbons of Examples 3 to 13 all have an effective magnetic permeability of 3730.
0 or more and the coercive force is 5.04 A / m or less, which indicates that the effective magnetic permeability is higher and the coercive force is lower than that of Comparative Example 4. The coercive force of the alloy ribbon of Example 14 was 4.32 A / m, which indicates that the coercive force was lower than that of Comparative Example 4. Further, B ₁₀ alloy ribbon of Example 3-14 is in the range of 1.53 to 1.56, are sufficiently large saturation magnetic flux density is obtained. From this, Fe
In Examples 3 to 14 using an alloy melt in which Y or a rare earth element is added to the Nb-B-based alloy by Nb substitution, the quenching causes the amorphous phase to contain Fe and B like Fe ₃ B in the amorphous phase. It is an alloy having a dual phase structure in which the crystal of the compound is precipitated. It can be seen that heat treatment of the alloy results in an alloy having excellent soft magnetic properties.

[0062] [Experimental Example 4] (Preparation 4 alloy thin _{strip) Fe 84 Nb 7-e B} 9 Nd e a composition
(e = 0 to 0.4 at% (atomic%)) The raw material prepared was subjected to high frequency melting in an N ₂ gas atmosphere, and the melted raw material was poured into a mold to obtain a mother alloy. Next, in a N ₂ gas atmosphere, the above-mentioned mother alloy is melted at a high frequency in a melt nozzle of an alloy ribbon manufacturing apparatus, and the obtained alloy melt is injected onto a cooling surface of a copper roll rotating at a high speed from a tip of a molten metal blowing part. When alloy ribbons were produced by the liquid quenching method of rapidly cooling the alloy, various alloy ribbons were obtained by producing the alloy ribbons under the following liquid quenching conditions 6 to 13. The composition of these alloy ribbons is Fe
_{84 Nb 7-e B 9 Nd} e (e = 0,0.04,0.08,
(0.15, 0.19 atomic%). The Nd (trace element) in the ribbon was analyzed by EDS.

In the liquid quenching conditions 6 to 9, the gap width at the tip of the molten metal blowing part of the molten metal nozzle is 0.2 mm,
The copper roll had an outer diameter of 20 cm. In the liquid quenching condition 6, the injection temperature was 1200 ° C. (1473 K) and the injection pressure was 392.
00Pa (0.4 kgf / cm ² ), back pressure -53200
Pa (-40cmHg), roll rotation speed 3600rpm
m, the roll peripheral speed was 38 m / s, and under the liquid quenching condition 7, the injection temperature was 1200 ° C. (1473 K), and the injection pressure was 3920.
0Pa (0.4kgf / cm ^2), the back pressure -53200P
a (-40 cmHg), roll rotation speed 3600 rpm,
The roll peripheral speed was set to 37.7 m / s, and under the liquid quenching condition 8, the injection temperature was 1200 ° C. (1473 K), and the injection pressure was 3920.
0Pa (0.4kgf / cm ^2), the back pressure -53200P
a (-40 cmHg), roll rotation speed 3600 rpm,
At a roll peripheral speed of 37.7 m / s, under the liquid quenching condition 9, the injection temperature was 1200 ° C. (1473 K), and the injection pressure was 3920.
0Pa (0.4kgf / cm ^2), the back pressure -53200P
a (-40 cmHg), roll rotation speed 3600 rpm,
The roll peripheral speed was 37.7 m / s.

In the liquid quenching conditions 10 to 13, the molten metal
Gap width of 0.25 at the tip of the molten metal outlet of the nozzle
mm and the outer diameter of the copper roll was 60 cm. Also, liquid quenching strip
In case 10, the injection temperature was 1350 ° C (1623K)
Pressure 68600Pa (0.7kgf / cm^Two), Back pressure-
79800 Pa (-60 cmHg), roll rotation speed 12
00 rpm, roll peripheral speed 37.7 m / s,
In the cold condition 11, the injection temperature was 1300 ° C (1573K),
Outlet pressure 83300 Pa (0.85 kgf / cm ^Two), Back
Pressure -79800 Pa (-60 cmHg), roll rotation speed
1250 rpm, roll peripheral speed 39.3 m / s, liquid
In the rapid cooling condition 12, the injection temperature was 1350 ° C. (1623
K), injection pressure 73500 Pa (0.75 kgf / cm
^Two), Back pressure -79800Pa (-60cmHg), low
1300 rpm, roll peripheral speed 40.8,
In the liquid quenching condition 13, the injection temperature was 1350 ° C. (1623
K), injection pressure 83300 Pa (0.85 kgf / cm
^Two), Back pressure -79800Pa (-60cmHg) roll
With rotation speed of 1400 rpm and roll peripheral speed of 44.0 m / s
It was done.

Next, the various alloy ribbons obtained were heated at a heating rate of 180 ° C./min (180 K
/ Min), followed by heat treatment at a retention time 5 minutes at the heat treatment temperature Ta below, a thickness of 20 [mu] m, various alloy ribbon width _{15mm (Fe 84 Nb 7-e} B 9 Nd e a composition (e = 0, 0.04,
0.08, 0.15 atomic%). Here, as the heat treatment temperature Ta, when the addition amount of Nd is 0 at%,
When the temperature is 75 ° C. (948 K) and the amount of Nd added is 0.04 at%, the temperature of 700 ° C. (973 K) and the amount of Nd added is 0.0
Those with 8 at% were set at 700 ° C. (973 K), and those with an added amount of Nd of 0.15 at% were set at 700 ° C. (973 K).

(Physical Properties of Alloy Strip) FIG.
Fe immediately after quenching obtained in 6-9₈₄Nb_7-eB₉Nd_eWhat
Composition (e = 0, 0.04, 0.08, 0.15 atom
%) Of alloy ribbon (alloy ribbon before heat treatment)
The result is shown. FIG. 4 shows the molten alloy under the above-mentioned quenching condition.
Crystallization temperature T when crystals precipitate when quenched_x1To
We show together. FIG. 5 shows the results obtained under the liquid quenching conditions 10 to 13.
Fe immediately after quenching₈₄Nb_7-eB₉Nd _eComposition (e =
0, 0.04, 0.08, 0.15 atom%)
7 shows the results of X-ray diffraction measurement of (alloy ribbon before heat treatment).
FIG. 5 shows that when the molten alloy is rapidly cooled under the above-described rapid cooling condition.
Crystallization temperature T when crystals precipitate_x1Are also shown.

As is clear from FIG.
The alloy ribbons obtained in (1) to (13) have a halo diffraction pattern peculiar to the amorphous phase, a (110) plane peak of a bcc phase (bcc-Fe) mainly composed of body-centered cubic Fe, and ( 200)
Since the peak of the surface is recognized, bcc is contained in the amorphous phase.
It can be seen that -Fe phase was precipitated. The alloy ribbons obtained under the liquid quenching conditions 10 to 13 are Fe ₈₄ N
When the amount of Nd added to the alloy having the composition of b ₇ B ₉ by Nb substitution is increased, the peaks of the (110) plane and the (200) plane of the bcc-Fe phase become large. All of the alloy ribbons obtained under the liquid quenching conditions 10 to 13 have the same crystal precipitation temperature T _x1 as 503 ° C. (776 K).

On the other hand, as is clear from FIG. 4, the alloy ribbons obtained under the liquid quenching conditions 8 to 9 have halo diffraction patterns unique to amorphous and diffraction patterns unique to Fe and B compound phases. (The peak shape formed in the vicinity of 47.5 ° to 57.5 is asymmetric), which indicates that Fe ₃ B crystals were precipitated in the amorphous phase. In addition, rapid cooling condition 8,
In the alloy ribbon of No. 9, the diffraction pattern unique to the body-centered cubic crystal was slightly recognized, and in addition to the Fe ₃ B crystal in the amorphous phase, bcc-
It can be seen that the peak of the (110) plane and the peak of the (200) plane of the Fe phase are also precipitated. In addition, liquid quenching condition 6 ~
The alloy ribbon obtained in No. 9 was obtained by increasing the amount of Nd added by Nb substitution to an alloy having a composition of Fe ₈₄ Nb ₇ B ₉ ,
The peak indicating the precipitation of Fe ₃ B crystals is large, and the crystal deposition temperature T increases with the increase in the amount of Nd added.
_It can be seen that _x1 is low. From these facts, even when the alloy ribbon has the same composition, if the liquid quenching conditions are different, the crystals precipitated in the amorphous phase are different, and
It can be seen that the crystallization temperatures are also different.

[0069] (Magnetic properties of the alloy ribbon) _{Next, Fe 84 Nb 7-e B} 9 obtained by liquid quenching conditions 6 to 9 Nd _e a composition (e = 0,0.04,0.08,0 The results of measuring the coercive force (Hc) and the effective magnetic permeability (μ) at 1 kHz after heat treatment of the alloy ribbon (.15 atomic%) are also shown in FIG. Further, Fe ₈₄ N obtained under liquid quenching conditions 10 to 13 was used.
b _7-e B ₉ Nd e a composition (e = 0,0.04,0.0
The results of measuring the coercive force (Hc) and the effective magnetic permeability (μ) at 1 kHz after the heat treatment of the alloy ribbon (8, 0.15 atomic%) are also shown in FIG.

From the results shown in FIGS.
Heat-treated alloy ribbons obtained in 0-13 are:
It can be seen that as the amount of Nd added increases, the effective magnetic permeability decreases and the coercive force increases. On the other hand, when the alloy ribbon obtained under the quenching conditions 6 to 9 is subjected to heat treatment,
It can be seen that when the added amount of d increases, the effective magnetic permeability can be increased, the coercive force can be reduced, and the soft magnetic properties are superior to those obtained by subjecting the alloy ribbon obtained under the quenching conditions 10 to 13 to a heat treatment. . The heat treatment of the alloy ribbons under the quenching conditions 8 and 9 has excellent soft magnetic properties because of the Fe—Nb—
When Nd added to the B-based alloy by Nb substitution increases, depending on the quenching condition, crystals of a compound of Fe and B like Fe ₃ B precipitate in the amorphous phase, and the compound of Fe and B
By promoting the generation of nuclei of cc-Fe crystals, bcc-F
It is considered that the crystal precipitation temperature T _x1 is lowered to _refine the crystal grains of e, and the number of fine bcc-Fe crystals precipitated by the heat treatment is increased, so that the soft magnetic characteristics can be improved.

(Heat Treatment Temperature Dependence of Magnetic Properties of Alloy Strip) Next, Fe ₈₄ Nb obtained under liquid quenching conditions 6 to 9 was used.
_7-e B ₉ Nd e a composition (e = 0,0.04,0.08,
FIG. 6 shows the results of measuring the magnetic properties when the heat treatment temperature applied to the alloy ribbon (0.15, 0.19 atomic%) was changed in the range of 625 ° C. (898K) to 750 ° C. (1023K). Nd in the composition of these alloy ribbons is represented by an EDS analysis value. _{Further, Fe 84 Nb 7-e B} 9 obtained by liquid quenching conditions 10 to 13 Nd _e a composition (e = 0,0.0
(0.08, 0.15 atom%) alloy heat treatment temperature to be applied to 625 ° C (898K) to 700 ° C (973K)
FIG. 7 shows the results of examining the magnetic characteristics when the magnetic field was changed in the range of FIG. Nd in the composition of these alloy ribbons is represented by an EDS analysis value. The magnetic characteristics here are based on the coercive force (H
c), effective magnetic permeability (μ), B ₁₀ (10 Oe (800 A
/ M) in an applied magnetic field. The effective magnetic permeability was measured using an impedance analyzer under the conditions of 5 mOe (400 mA / m), 1 k
Hz. Coercivity and B ₁₀ were measured using a DC B-H loop tracer.

From the results shown in FIGS. 6 and 7, the alloy ribbons obtained under the liquid quenching conditions 10 to 13 were subjected to a heat treatment temperature of 625 ° C.
From (898 K) to 675 ° C. (948 K), the effective magnetic permeability at B ₁₀ and 1 kHz increases with an increase in the heat treatment temperature for any of the added amounts of Nd, and the coercive force hardly changes. The coercive force exceeds 8 A / m when the amount of Nd added is other than 0 at%, but the heat treatment temperature is 675.
C. (948 K), the amount of Nd added is 0.04a
and t%, those of 0.08at%, B ₁₀ and the effective permeability is decreased, the coercive force is increased.

On the other hand, the alloy ribbons obtained under the liquid quenching conditions 6 to 9 are heat-treated at 625 ° C. (898 K) to 70 ° C.
Up to 0 ° C. (973 K), the effective magnetic permeability at B ₁₀ and 1 kHz increases and the coercive force decreases with increasing the heat treatment temperature for all the Nd added amounts.
Heat treatment temperatures of 650 ° C. (923K) to 700 ° C. (97 ° C.)
3K) is as small as 8 A / m or less. When the heat treatment temperature exceeds 700 ° C. (973 K), B ₁₀ and the effective magnetic permeability of the alloy ribbon obtained under the liquid quenching conditions 6 to 9 decrease, and the coercive force increases. When the amount of Nd quenched under the liquid quenching condition 8 is 0.08 at%, an effective magnetic permeability of about 20,000 or more is obtained even at a heat treatment temperature of 625 ° C. (898 K).
At 75 ° C. (948 K), an effective magnetic permeability of about 27500 or more is obtained. Nd quenched under liquid quenching condition 9
Is 0.15 at%, the heat treatment temperature is 62
An effective magnetic permeability close to 30,000 is obtained even at 5 ° C. (898K), and an effective magnetic permeability exceeding 30,000 is obtained at a heat treatment temperature of 675 ° C. (948K). From these facts, it can be seen that when Nd is added, a compound of Fe and B precipitates depending on the liquid quenching condition, and the magnetic permeability can be increased even in a range where the heat treatment temperature is low.

[0074]

As described above, in the soft magnetic alloy having a fine crystalline structure according to the present invention, the structure after quenching the molten alloy has an amorphous phase and a compound phase of Fe and B or an amorphous phase and an F phase.
An alloy having a multiphase structure composed of a compound phase of e and B and a bcc-Fe phase (mainly Fe crystal grains having a body-centered cubic structure) is subjected to a heat treatment to form fine bcc-Fe phase crystal grains. Since the alloy structure is precipitated, the alloy structure after quenching the alloy melt has a compound phase of Fe and B or a compound phase of Fe and B and a double phase structure in which a bcc-Fe phase is precipitated in addition to the amorphous phase. And the compound of Fe and B is bcc-
In order to promote the generation of Fe crystal nuclei and to refine the bcc-Fe crystal grains, the crystal deposition temperature is lowered.
The number of fine bcc-Fe crystal grains precipitated by heat treatment is increased, and high magnetic permeability and low coercive force can be obtained.
Soft magnetic characteristics can be improved. Further, the method for producing a soft magnetic alloy having a fine crystal structure according to the present invention is characterized in that the alloy melt is quenched to form an amorphous phase and a compound phase of Fe and B or an amorphous phase and a compound phase of Fe and B and bcc After forming an alloy having a dual phase structure composed of an Fe phase, the alloy is subjected to a heat treatment to precipitate fine bcc-Fe phase crystal grains. It is suitably used for producing soft magnetic alloys.

[Brief description of the drawings]

FIG. 1. F immediately after quenching obtained under liquid quenching conditions 1-2
and X-ray diffraction results of the alloy ribbon e ₈₄ Nb _6.85 B ₉ Nd _0.15 a composition (EDS analysis value) is a diagram showing the magnetic properties after the heat treatment of these alloy ribbons.

FIG. 2 Fe ₈₄ immediately after quenching obtained under each liquid quenching condition
And results of the Nb _6.92 B ₉ Nd _{0.0 8} having a composition (EDS analysis) X-ray diffraction measurement of the alloy ribbon is a diagram showing the magnetic properties after the heat treatment of these alloy ribbons.

FIG. 3 Fe ₈₄ immediately after quenching obtained under each liquid quenching condition
Nb _6.9 R _0.1 B ₉ (R = Y, La, Ce, Nd, Sm)
Alloy ribbon of different composition (input composition), Fe ₈₄ N immediately after quenching
b _6.8 R _0.2 B ₉ (R = Pr) An alloy ribbon having a composition (input composition), an X-ray diffraction result of an alloy ribbon having a composition of Fe ₈₄ Nb ₇ B ₉ immediately after quenching, and these alloy ribbons. FIG. 4 is a view showing magnetic properties after heat treatment of FIG.

FIG. 4: F immediately after quenching obtained under liquid quenching conditions 6 to 9
e₈₄Nb_7-eB₉Nd _eComposition (e = 0, 0.04, 0.
08, 0.15 atom%) (EDS analysis value)
(Results of X-ray diffraction measurement of alloy ribbon before heat treatment)
It is a figure which shows the magnetic characteristic after heat processing of these alloy ribbons.

[5] _{Fe 84 Nb 7-e B 9} Nd e a composition immediately after quenching obtained in the liquid quenching conditions 10~13 (e = 0,0.04,
FIG. 4 shows the results of X-ray diffraction measurement of alloy strips (0.08, 0.15 atomic%) (EDS analysis values) (alloy strips before heat treatment) and magnetic properties of these alloy strips after heat treatment. It is.

FIG. 6: Fe ₈₄ Nb obtained under liquid quenching conditions 6 to 9
_7-e B ₉ Nd e a composition (e = 0,0.04,0.08,
The heat treatment temperature applied to the alloy ribbon of (0.15, 0.19 atomic%) (EDS analysis value) is 625 ° C. (898K) to 750 ° C.
It is a figure which shows the magnetic characteristic at the time of changing in the range of (1023K).

FIG. 7: Fe ₈₄ N obtained under liquid quenching conditions 10 to 13
b _7-e B ₉ Nd e a composition (e = 0,0.04,0.0
(0.15 atomic%) (EDS analysis value), the heat treatment temperature applied to the alloy ribbon is from 625 ° C. (898K) to 700 ° C. (97 ° C.).
It is a figure which shows the magnetic characteristic when changing in the range of 3K).

Claims (11)

[Claims] 1. The structure after quenching a molten alloy is composed of an amorphous phase and a compound phase of Fe and B or a double phase structure composed of an amorphous phase, a compound phase of Fe and B, and a bcc-Fe phase. A soft magnetic alloy having a fine crystal structure, wherein a heat treatment is applied to the resulting alloy to precipitate fine bcc-Fe phase crystal grains. 2. The soft magnetic alloy having a fine crystalline structure according to claim 1, wherein the soft magnetic alloy is represented by the following composition formula. _{T 100-abc M a X b} Nb c where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
X represents at least one element among W, Cr, X represents one or more elements containing at least B among B, P, and C, and a, b, and c indicating composition ratios are atomic%; 0 ≦ a ≦
3, 2 ≦ b ≦ 18 and 4 ≦ c ≦ 8. 3. The soft magnetic alloy having a fine crystal structure according to claim 1, wherein the soft magnetic alloy is represented by the following composition formula. _{T 100-abcde M a X b} Nb c M 'd Z e where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
W represents at least one element of Cr, X represents one or more elements containing at least B of B, P, and C, and M ′ represents one of Pt, Au, Pd, Ag, and Cu. Z represents Zr, Ti, H
a, b, c, d, and e, which represent at least one of f, Al, Y, and rare earth elements, and indicate the composition ratio, are atomic%, and 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, 4 ≦ c ≦ 8, 0 <
d ≦ 3 and 0 ≦ e ≦ 3. 4. The soft magnetic alloy having a fine crystal structure according to claim 1, wherein the soft magnetic alloy is represented by the following composition formula. T _100-abcef M _a X _b N _{b c} Z _e G a _f where T represents one or more elements including at least Fe among Fe, Co, and Ni, and M represents V, Mn, Mo, Ta,
X represents at least one element among W, Cr, X represents one or more elements containing at least B among B, P, and C, and Z represents Zr, Ti, Hf, Al, Y, and a rare earth element. A, b, c, e, and f, which represent at least one element among the above, and indicate the composition ratio, are atomic%, and 0 ≦ a ≦ 3, 2 ≦
b ≦ 18, 4 ≦ c ≦ 8, 0 ≦ e ≦ 3, and 0 <f ≦ 3. 5. The soft magnetic alloy having a fine crystalline structure according to claim 1, wherein the soft magnetic alloy is represented by the following composition formula. _{T 100-abcdef M a X b} Nb c M 'd Z e Ga f where, T is expressed Fe, Co, one or more elements including at least Fe of Ni, M is V, Mn, Mo, Ta,
W represents at least one element of Cr, X represents one or more elements containing at least B of B, P, and C, and M ′ represents one of Pt, Au, Pd, Ag, and Cu. Z represents Zr, Ti, H
a, b, c, d, e, f representing at least one of f, Al, Y and rare earth elements
Is atomic%, 0 ≦ a ≦ 3, 2 ≦ b ≦ 18, 4 ≦ c ≦ 8,
0 <d ≦ 3, 0 ≦ e ≦ 3, and 0 <f ≦ 3. 6. a, b, c indicating a composition ratio in the composition formula
Is atomic%, 0.1 ≦ a ≦ 1, 8 ≦ b ≦ 13, 5 ≦ c ≦
7. The soft magnetic alloy having a fine crystal structure according to claim 2, wherein the soft magnetic alloy has a fine crystal structure. 7. In the above composition formula, d representing a composition ratio is atomic%.
The soft magnetic alloy having a fine crystal structure according to claim 3, wherein 0 <d ≦ 0.1. 8. In the above composition formula, e representing a composition ratio is atomic%.
Wherein 0 <e ≦ 2.
A soft magnetic alloy having a fine crystal structure according to any one of the above. 9. In the above composition formula, f indicating a composition ratio is atomic%.
And wherein 0 <f ≦ 1.
A soft magnetic alloy having a fine crystal structure according to any one of the above. 10. The soft magnetic alloy having a fine crystal structure according to claim 1, wherein the soft magnetic alloy having a fine crystal structure has an effective magnetic permeability at 1 kHz of 33,000 or more. . 11. An alloy having a double-phase structure composed of an amorphous phase and a compound phase of Fe and B or an amorphous phase, a compound phase of Fe and B and a bcc-Fe phase by rapidly cooling the molten alloy. Forming a soft magnetic alloy having a fine crystal structure, wherein the alloy is subjected to heat treatment to precipitate fine bcc-Fe phase crystal grains.