JP2003041353A - Fe-BASED SOFT MAGNETIC ALLOY - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a Fe-based soft magnetic alloy, which can improve amplitude permeability while keeping a high saturated magnetic-induction density, raise a blowing temperature of a molten metal, and blow it without clogging a nozzle. SOLUTION: The Fe-based soft magnetic alloy is characterized by having a composition shown by either formula of (Fe1-a Za )b Bx My Qz or (Fe1-a Za )b Bx My Qz Xt , where Z indicates one or two elements of Ni and Co, M indicates one or more elements selected among Ti, Zr, Hf, V, Nb, Ta, Mo, and W, Q indicates one or more rare-earths elements including Y, and a, b, x, y, and z indicate component ratios and are in ranges of, by atom.%, 0<=a<=0.2, 75<=b<=93, 0.5<=x<=18, 4<=y<=9, and 0<z<=0.5, and where in the second composition formula, t indicates the component ratio and is in a range of 0<t<=5, by atom.%, beside satisfying the above composition ratios.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high permeability Fe-based soft magnetic alloy used for magnetic heads, transformers, choke coils and the like.

[0002]

2. Description of the Related Art In soft magnetic alloys used for magnetic heads, transformers, choke coils, etc., various characteristics generally required are as follows. High saturation magnetic flux density. High magnetic permeability. Must have low coercive force. Therefore, when manufacturing soft magnetic alloys or magnetic heads, various alloy systems have been studied from these viewpoints. Conventionally, crystalline alloys such as sendust (Fe-Si-Al alloy), permalloy (Fe-Ni alloy), and silicon steel have been used for the above-mentioned applications.
Amorphous e- and Co-based alloys are also being used.

[0003]

However, in the case of a magnetic head, a more suitable magnetic material for a high-performance magnetic head is desired in order to cope with a high coercive force of a magnetic recording medium accompanying a high recording density. . Further, in the case of transformers and choke coils, miniaturization is required as electronic devices are miniaturized. Therefore, high-performance magnetic materials are desired. However,
Although the above-mentioned sendust has excellent soft magnetic characteristics, it has a drawback that the saturation magnetic flux density is as low as about 11 kG. Similarly, permalloy also has a low saturation magnetic flux density of about 8 kG in an alloy composition having excellent soft magnetic characteristics. Silicon steel has a drawback that it has a high saturation magnetic flux density but a poor soft magnetic property.

Further, among the above-mentioned amorphous alloys, the Co-based alloy is excellent in soft magnetic characteristics, but the saturation magnetic flux density is insufficient at about 10 kG. Further, the Fe-based alloy has a high saturation magnetic flux density and can have a magnetic flux density of 15 kG or more, but the soft magnetic characteristics are insufficient. Further, the thermal stability of the amorphous alloy is not sufficient, and there are still unsolved aspects. As mentioned above, it is difficult to combine high saturation magnetic flux density with excellent soft magnetic characteristics.

Therefore, the inventors of the present invention have proposed a high saturation magnetic flux density Fe-based soft magnetic alloy which solves the above-mentioned problems.
A patent application has been filed in Japanese Patent No. 49 (Japanese Patent Application No. 2-108308). One of the alloys according to this patent application is characterized by having a composition represented by the following formula: high saturation magnetic flux density F
It was an e-based soft magnetic alloy. (Fe _1-f Co _f ) _g B _h T _1i T _2j where T ₁ is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains one or both of Zr and Hf, and T ₂ is Cu, Ag, Au, Ni, Pd, Pt. F is one or more elements selected from the group consisting of
≦ 0.05, g ≦ 92 atomic%, h = 0.5 to 16 atomic%, i
= 4 to 10 atom%, j = 0.2 to 4.5 atom%. Further, another one of the alloys according to the above patent application is a high saturation magnetic flux density alloy characterized by having a composition represented by the following formula. Fe _g B _h T _1i T _2j where T ₁ is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains either or both of Zr and Hf, and T ₂ is Cu, Ag, Au, Ni, Pd, Pt. 1 or 2 or more elements selected from the group consisting of
≦ 92 atomic%, h = 0.5 to 16 atomic%, i = 4 to 10 atomic%, and j = 0.2 to 4.5 atomic%.

Next, the inventors of the present invention have proposed, as an advanced alloy of the above-mentioned alloy, JP-A-4-333546 (Japanese Patent Application No. 2-2).
No. 30135), a patent application has been filed for an alloy having the following composition. One of the alloys in this patent application
The second was an alloy having a high saturation magnetic flux density, which was characterized by having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x T _y where, Q is Co, where any or both of Ni, T
Is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W, and contains either or both of Zr and Hf, and a ≤
0.05, b ≦ 93 at%, x = 0.5-8 at%, y =
It is 4 to 9 atom%. Another one of the alloys according to the above patent application is characterized by having a composition represented by the following formula. Fe _b B _x T _y However, T is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from the group consisting of W, and containing either or both of Zr and Hf, b
≦ 93 at%, x = 0.5 to 8 at%, y = 4 to 9 at%.

By the way, a soft magnetic alloy is used for a magnetic head or a transformer.
When using it as a core material for a sensor, etc., use a liquid quenching method etc.
The soft magnetic alloy ribbon manufactured by
Various processing such as insulation processing that stacks and coats this with resin
It is used after being applied. However, JP-A-5-93
No. 249 (Fe_1-fCo_f)_g B_h T_1i T_2jComposition
Soft magnetic alloy, Fe_g B_h T_1i T_2jSoft magnetism of composition
Alloy, (Fe described in JP-A-4-333546)
_1-aQ_a)_b B_x T_yFe, a soft magnetic alloy of the following composition_b B_x T
_yWhen using a ribbon made of soft magnetic alloy of
In addition, when the resin for insulation is cured and contracted, the soft magnetic
A compressive stress is applied to the core made of a magnetic alloy, causing magnetostriction.
As a result, the magnetic properties change and the target magnetic properties are obtained.
There was a problem that it was difficult to obtain things.

Therefore, the inventors of the present invention further researched the soft magnetic alloy described in Japanese Patent Application Laid-Open No. 5-93249 filed previously, and among the elements added to these systems, Si and A
An Fe-based soft magnetic alloy whose magnetostriction can be adjusted by solid-solving an element selected from l, Ge, and Ga in a bcc phase containing Fe as a main component is disclosed in JP-A-9-360.
A patent application has been filed in No. 8 (Japanese Patent Application No. 7-147838). However, in the Fe-based soft magnetic alloy described in JP-A-9-3608, an element selected from Si, Al, Ge, and Ga is contained in the bcc phase (body-centered cubic crystal phase) containing Fe as a main component. Since it is a solid solution, impurities are mixed in the body-centered cubic crystal phase, and the concentration of Fe, Ni, and Co in the soft magnetic alloy decreases greatly, and the saturation magnetic flux density and magnetic permeability are There was a problem that it would decrease.

Next, Fe and B, which were previously filed by the present inventors, were applied.
In order to produce a component-based Fe-based soft magnetic alloy mainly composed of the element T and the element T, an alloy melt having a desired composition is prepared, housed in a crucible, and rotated in a non-oxidizing atmosphere. It is necessary to employ a super-quenching method in which molten metal is blown out from the ejection port of the crucible and rapidly cooled into a ribbon shape. This is because even if an attempt is made to produce a molten FeBM alloy in the atmosphere by the ultra-quenching method, the ribbon is easily oxidized and it is difficult to obtain a uniform ribbon. Further, if the temperature at which the molten metal is blown out is lowered, the viscosity of the molten metal is reduced, and the expensive quartz jet nozzle used for blowing out this type of Fe-based soft magnetic alloy may be clogged, leading to the destruction of the nozzle. Was. Therefore, it is preferable to blow out the molten metal at the time of blowing this kind of Fe-based soft magnetic alloy as high as possible, but if the blowing temperature is raised, the compound phase is likely to precipitate on the obtained ribbon, and the amorphous However, even if the amorphous ribbon is heat-treated, the compound phase remains and the soft magnetic characteristics deteriorate.

The present invention has been made in view of the above circumstances, and it is possible to obtain a magnetic permeability while maintaining a high saturation magnetic flux density, and it is possible to raise the temperature when the molten metal is blown out, and It is possible to blow out without applying a load to the nozzle, and it is possible to obtain a high-quality amorphous alloy ribbon, and by crystallizing on this basis, an Fe-based soft magnetic alloy with good soft magnetic properties is provided. The purpose is to provide the technology that can.

[0011]

In order to achieve the above object, the present invention provides an Fe-based soft magnetic alloy represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y Q z , however, Z is Ni, 1 kind or two elements of Co,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W, and Q is one or more elements of rare earth elements including Y. And
The composition ratios a, b, x, y, and z are 0 ≦ a ≦ 0.2,
75 atom% ≦ b ≦ 93 atom%, 0.5 atom% ≦ x ≦ 18
Atomic%, 4 atomic% ≦ y ≦ 9 atomic% and 0 <z ≦ 0.5 atomic%.

Further, in order to achieve the above object, the present invention provides a Fe-based soft magnetic alloy represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y Q z X t However, Z is Ni, 1 kind or two elements of Co,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W, and Q is one or more elements of rare earth elements including Y. , X is one or more elements selected from Si, Al, Ge, Ga, P, C and Cu, and a, b, x, which indicate the composition ratio,
y, z and t are 0 ≦ a ≦ 0.2 and 75 atomic% ≦ b ≦ 93
Atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y
≦ 9 atomic%, 0 <z ≦ 0.5 atomic%, 0 <t ≦ 5 atomic%
Is.

As means for controlling the volume fraction of the crystalline phase and the amorphous phase, one or more elements Q selected from rare earth elements including Y are elements having an amorphous forming ability. Therefore, the addition of the element Q promotes the ability to generate crystal nuclei having a fine crystal structure, and the addition of a small amount causes an improvement in soft magnetic characteristics.

The element Q is (Fe or Fe-
Z) -BM system alloy or (Fe or Fe-Z) -B
The soft magnetic properties can be improved by adding a small amount to the -MT alloy, so Fe and C in the soft magnetic alloy can be improved.
Since the decrease in the concentrations of o and Ni is small, the saturation magnetic flux density can be kept high. Further, since the element Q has a high ability to form an amorphous phase, the addition of the element Q allows the amorphous phase to be formed even if the amount of B or the element M added is reduced. For example, the addition amount of the element M can be set to slightly exceed 4 atom%, so that the Fe, Co, and Ni concentrations are relatively high, and high saturation magnetic flux density can be achieved. This is because the element Q does not form a solid solution in the bcc phase (body-centered cubic phase) containing Fe as a main component and remains in the amorphous phase, so that it does not become an impurity and is similar to B and M. Since it has the ability to form an amorphous material, the amount of B or M added can be reduced accordingly. Furthermore, the addition of the element Q raises the Curie temperature of the remaining amorphous phase, so that the soft magnetic characteristics can be improved.

In the Fe-based soft magnetic alloy of the present invention, the element M in the composition formula preferably contains Nb. When Mb in the composition formula contains Nb, the cost can be kept low while maintaining the effect of reducing the growth rate of fine crystal nuclei and the amorphous forming ability. Further, since Nb is less likely to be oxidized than Zr or Hf, it can be made less likely to be oxidized, and the Fe-based soft magnetic alloy can be easily manufactured.

In the Fe-based soft magnetic alloy of the present invention, the element Q in the above composition formula is Y, La, Ce, Pr, Nd, D.
It is preferable that at least one or more of y and Tb are contained. In addition, in the Fe-based soft magnetic alloy of the present invention, it is preferable that the element Q in the composition formula contains at least one of La and Ce. La
Since Ce and Ce are cheaper than Y, Pr, Nd, Dy, Tb, etc., by using La and / or Ce as the element Q in the above composition formula, the addition effect of the above-mentioned element Q can be obtained and low. Can be a cost. In addition, in the Fe-based soft magnetic alloy of the present invention, it is preferable that the element Q in the composition formula is misch metal or contains misch metal. The misch metal mainly contains La and / or Ce, and contains a small amount of other rare earth elements such as Nd, and is used as a raw material for the rare earth element. ) Is purified to produce each rare earth element. Since this misch metal is inexpensive, by using misch metal as the element Q or by including misch metal as the element Q, the above-described effect of adding the element Q can be obtained and the cost can be reduced. Further, in the Fe-based soft magnetic alloy of the present invention, z representing the composition ratio in the composition formula is 0 <z ≦ 0.5 atom%. A high saturation magnetic flux density can be obtained when the addition amount of Q is in the range of 0.01 atom% or more and 0.5 atom% or less. Further, in the Fe-based soft magnetic alloy of the present invention, y indicating the composition ratio in the above composition formula
Is preferably 4 atom% ≦ y ≦ 9 atom% from the viewpoint of improving the amorphous forming ability.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the Fe-based soft magnetic alloy of the present invention will be described below. The Fe-based soft magnetic alloy of the present invention is represented by any of the following composition formulas. _{(Fe 1-a Z a)} b B x M y Q z (Fe 1-a Z a) b B x M y Q z X t

However, Z is one or two of Ni and Co.
Species element, M is Ti, Zr, Hf, V, Nb, Ta, M
One or more of O and W, Q is a rare earth element containing Y (Y, La, Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b, Lu), one or more elements selected from the group consisting of
The composition ratios a, b, x, y, and z are 0 ≦ a ≦ 0.2,
75 atom% ≦ b ≦ 93 atom%, 0.5 atom% ≦ x ≦ 18
Atomic%, 4 atomic% ≦ y ≦ 9 atomic% and 0 <z ≦ 0.5 atomic%. Further, in the Fe-based soft magnetic alloy of the present invention,
T may be added to the aforementioned Fe or Fe-Z, B, M, and Q, in which case T is Si, Al, Ge, G.
It is one or more elements selected from a, and t representing the composition ratio is 0 ≦ t ≦ 5 atomic%.

The Fe-based soft magnetic alloy of the present invention having the above composition has a body-centered cubic structure (bcc) with an average crystal grain size of 30 nm or less.
(Structure) mainly composed of a microcrystalline phase composed of Fe crystal grains,
Since it has a structure composed of the microcrystalline phase and the amorphous phase, it can maintain a high saturation magnetic flux density and a high magnetic permeability, and is used in a magnetic head, a transformer, a choke coil or the like. It is suitable as a material. In addition, the Fe-based soft magnetic alloy of the present invention can improve the soft magnetic characteristics by adjusting the type and the addition amount of the element Q.

In the composition system of the Fe-based soft magnetic alloy used in the present invention, the main components Fe, Co, and Ni are elements that play a role in magnetism, and in order to obtain a high saturation magnetic flux density and excellent soft magnetic characteristics. is important. In soft magnetic alloys of these compositions, the value of b indicating the amount of addition of Fe, or Fe
And the value of b indicating the total amount of Co and / or Ni added is 93 atomic% or less. When Fe exceeds 93 atom%, it becomes difficult to obtain an amorphous single phase by the liquid quenching method, and as a result, the structure of the alloy obtained after the heat treatment becomes nonuniform, and it is difficult to obtain high magnetic permeability. Therefore, it is not preferable. On the other hand, if Fe is less than 75 atomic%, a saturation magnetic flux density (Bs) of 1 T (tesla) or more cannot be obtained, which is not preferable. Therefore, the range of Fe is 75 atomic% ≤ b ≤ 9
It was 3 atomic%. Further, a part of Fe may be replaced with one or two elements Z of Co and Ni for adjusting magnetostriction and the like, and in this case, it is preferably 20% or less of Fe. . If it is out of this range, the magnetic permeability deteriorates.
Therefore, in the above composition formula, the composition ratio a of Z is preferably 0.2% or less.

B has the effect of increasing the amorphous forming ability of the soft magnetic alloy, the effect of preventing the coarsening of the crystal structure, and the effect of suppressing the formation of the compound phase that adversely affects the magnetic properties in the heat treatment process. Conceivable. In addition, Zr, Hf,
It is said that Nb hardly forms a solid solution with α-Fe, but by rapidly cooling the alloy to make it amorphous, Zr and Hf or Nb are dissolved in α-Fe in a supersaturated state. The amount of solid solution of these elements is adjusted by the heat treatment to be partially crystallized and precipitated as a fine crystalline phase, which has the effect of improving the soft magnetic properties of the obtained soft magnetic alloy.

Further, in order to precipitate the fine crystal phase and suppress the coarsening of the crystal grains of the fine crystal phase, it is necessary to leave the amorphous phase, which may hinder the crystal grain growth, at the grain boundary. it is conceivable that. Further, this grain boundary amorphous phase is the Zr and H which are discharged from α-Fe due to the rise of the heat treatment temperature.
It is considered that the solid solution of the element M such as f and Nb suppresses the generation of the Fe-M compound that deteriorates the soft magnetic characteristics. Therefore, it is important to add B to the Fe-Zr (Hf, Nb) alloy.

If x, which indicates the amount of B added, is less than 0.5 atomic%, the amorphous phase at the grain boundaries becomes unstable, and a sufficient effect cannot be obtained. When x exceeds 18 atomic%,
In the B-M system and the Fe-B system, the boride formation tendency becomes strong, the heat treatment conditions for obtaining a fine crystal structure are restricted, and good soft magnetic properties cannot be obtained. In this way, by adjusting the amount of B added appropriately, the average crystal grain size of the precipitated fine crystal phase can be adjusted to 30 nm or less.

In order to easily obtain the amorphous phase,
It is preferable to contain any one of Zr, Hf, and Nb, which has a particularly high amorphous forming ability, and a part of Zr, Hf, and Nb may be contained in other 4
It can be replaced with any one of Ti, V, Ta, Mo and W among the elements of the A to 7A groups. In addition, Zr, Hf, N
Among b, Hf is an extremely expensive element, so it is more preferable to include Nb in consideration of the raw material cost. The element M is a relatively slow diffusion species, and the addition of the element M has the effect of reducing the growth rate of fine crystal nuclei.
It is considered to have the ability to form an amorphous substance, and is effective for making the structure fine.

When y, which indicates the amount of addition of the element M, is 4 atomic% or less, the effect of reducing the nucleus growth rate is lost, and the crystal grain size becomes coarse, making it difficult to obtain good soft magnetism. Also, Fe
In the case of the —Hf—B system alloy, the average crystal grain size at Hf = 5 atomic% is 13 nm, whereas it is 3 at Hf = 3 atomic%.
Coarsening to 9 nm. When y, which indicates the amount of addition of the element M, exceeds 9 atomic%, the formation tendency of the MB-type or Fe-M-type compound increases, and good characteristics cannot be obtained.

Among them, Nb, Mo, and W have a small absolute value of free energy for forming an oxide, are thermally stable, and hardly form an oxide. Therefore, when manufacturing a soft magnetic alloy by adding these elements, the entire atmosphere at the time of manufacturing is not an inert gas atmosphere but an atmosphere of the atmosphere, or of a crucible nozzle used when quenching the molten metal. Since the tip can be manufactured in the atmosphere while supplying an inert gas, the manufacturing conditions are facilitated, and the magnetic core material and the like used for the above-described applications can be manufactured at low cost. The addition amount of the element M is 4 atomic% or more, 9 atomic%
The following is preferable in that the amorphous forming ability is improved.

Further, in the composition of the present invention, in order to realize a high magnetic permeability and a low coercive force while maintaining a high saturation magnetic flux density, one or more elements Q of rare earth elements including Y are contained. Has been. As the element Q used here,
Y, La, Ce, Pr, Nd, Dy, Tb, Pm, S
It is preferable to contain at least one or two or more of m, Eu, Gd, Ho, Er, Tm, Yb, and Lu.

The reason is that, by adding the element Q, nuclei of fine crystals are easily generated, and it is possible to increase the magnetic permeability after heat treatment and decrease the low coercive force. Thus, the addition of the element Q improves the soft magnetic characteristics.

The element Q is (Fe or Fe-
Z) -BM system alloy or (Fe or Fe-Z) -B
Since the improvement of the soft magnetic properties is caused by adding a small amount to the -MT alloy, Fe and Co in the soft magnetic alloy are added.
Since the decrease in the concentration of Ni and Ni is small, the saturation magnetic flux density can be kept high. Further, since the element Q has an amorphous forming ability, the addition of the element Q causes B
Since the amount of addition of M and M can be reduced, the Fe concentration can be relatively increased and the saturation magnetic flux density can be increased. Since the element Q does not form a solid solution in the bcc phase (body-centered cubic phase) containing Fe as a main component and remains in the amorphous phase, it does not become an impurity, and B or M
This is because it plays the same role as, and the amount of B or M added can be reduced accordingly. Further, the element Q has a function of increasing the Curie temperature of the residual amorphous phase, and thereby the soft magnetic characteristics can be improved. In the composition of the present invention, the element Q preferably contains at least one of La and Ce. La and C
Since e is cheaper than Y, Pr, Nd, Dy, Tb, etc., La and / or C is used as the element Q in the above composition formula.
By using e, the effect of adding the above-mentioned element Q can be obtained and the cost can be reduced. Further, in the composition of the present invention, the element Q in the composition formula is preferably misch metal or contains misch metal. Misch metal (MN) is La and / or C
e is mainly contained, and other rare earth elements such as Nd are contained in a trace amount, which is used as a raw material of the rare earth element, and each rare earth element is refined by refining this raw material (Misch metal). Manufactures elements. Since this misch metal is inexpensive, by using misch metal (MN) as the element Q or by including misch metal as the element Q, the above-described effect of adding the element Q is obtained and the cost is low. it can.

Z, which indicates the added amount of the element Q, is 0 <z ≦ 0.
5 atom%, preferably 0.05 atom% ≦ z ≦ 0.4 atom%
Is. This is because when the addition amount of Q is in the range of 0.05 atom% or more and 0.4 atom% or less, both high saturation magnetic flux density and excellent soft magnetic properties can be provided. The soft magnetic alloy of the present invention may contain 0 or more and 5 at% or less of the element T of one or more of Si, Al, Ge, and Ga. These are known as metalloid elements and are solid-solved in a body-centered cubic phase containing Fe as a main component. If the content of these elements exceeds 5 atomic%, the magnetostriction increases, the saturation magnetic flux density decreases, or the magnetic permeability decreases, which is not preferable.

The element T has the effect of increasing the electric resistance of the soft magnetic alloy and decreasing the iron loss, but Al has a large effect. Further, Ge and Ga have the effect of making the diameter of the crystal grains smaller. Therefore, among Si, Al, Ge, and Ga, the effect of adding Al, Ge, and Ga is particularly large.
More preferably, 1, 1, Ge, and Ga are added individually, or Al and Ge, Al and Ga, Ge and Ga, and Al and Ge and Ga are added together.

In the soft magnetic alloy having the above composition,
Zn, Cd, In, Sn, Pb, As, S as required
b, Bi, Se, Te, Li, Be, Mg, Ca, S
It is also possible to adjust the magnetostriction of the soft magnetic alloy by adding an element such as r or Ba. In the soft magnetic alloy having the above composition, even if the unavoidable impurities such as H, N, O, and S are contained to the extent that the desired characteristics are not deteriorated, the composition is the same as that of the Fe-based soft magnetic alloy used in the present invention. Of course, it can be considered.

To produce the Fe-based soft magnetic alloy of the present invention, for example, a (Fe or Fe-Z) -BM system or a (Fe or Fe-Z) -B-M-T system amorphous is prepared. Alloy or crystalline alloy containing amorphous phase (where Z is Ni, C
one or more elements out of o, M is Ti, Zr,
One or two or more elements selected from Hf, V, Nb, Ta, Mo, and W, and T is one or more elements selected from Si, Al, Ge, and Ga. ) Is melted by means of arc melting, high frequency induction melting, etc. to rapidly cool the alloy melt to prepare a ribbon having an amorphous phase as a main component, and a rare earth containing Y in the alloy melt. One or more elements Q selected from the elements are added, and the type and the amount of the element Q added at this time are adjusted. Here, as a specific method for producing the ribbon, a submerged spinning method as described in JP-A-4-323351 or a quenching method using a single roll can be adopted. By these methods, a ribbon-shaped ribbon having an amorphous phase as a single phase or an amorphous phase as a main component can be obtained.

Then, by heat-treating the produced ribbon, a part of the amorphous phase of the ribbon is crystallized, and the amorphous phase and F of the fine bcc structure having an average grain size of 30 nm or less are obtained.
A structure in which a fine crystal phase composed of crystal grains of e is mixed is obtained, and the target Fe-based soft magnetic alloy is obtained.

The fine crystal structure composed of fine Fe crystal grains having a bcc structure with an average crystal grain size of 30 nm or less was precipitated by the heat treatment because the amorphous alloy ribbon in the rapidly cooled state was mainly composed of the amorphous phase. It is a tissue that does, and when this is heated,
This is because a fine crystal phase composed of crystal grains having a body-centered cubic structure containing Fe as a main component and having an average crystal grain size of 30 nm or less at a certain temperature or higher is precipitated. The temperature at which the fine crystalline phase composed of Fe crystal grains having the bcc structure is deposited is about 480 to 550 ° C., depending on the composition of the alloy. Further, at a temperature higher than the temperature at which the fine crystal phase of Fe is precipitated, Fe ₃
B etc., or Fe ₃ Z when the alloy contains Zr
A compound phase such as r that deteriorates the soft magnetic characteristics is deposited. The temperature at which such a compound phase is precipitated depends on the composition of the alloy, but is about 740 to 810 ° C. However, the above Fe ₃ B
Etc., it is possible to obtain a state in which the magnetic properties are excellent even if they are precipitated. Therefore, it is possible to partially precipitate a compound phase such as Fe ₃ B.

Therefore, in the present invention, the holding temperature when heat-treating the amorphous alloy ribbon or the like is 480 ° C to 810 ° C.
Within the range, it is preferably set in accordance with the composition of the alloy so that the fine crystal phase mainly composed of Fe crystal grains having a body-centered cubic structure is preferably precipitated and the compound phase is not precipitated.

The temperature rising rate when the temperature is raised to the heat treatment temperature is preferably 20 to 200 ° C./min, and 40 to
The range of 200 ° C./minute is more preferable. Since the manufacturing time becomes long when the heating rate is slow, it is preferable that the heating rate is fast, but in view of the performance of the heating device, the upper limit is about 200 ° C./minute.

The holding time of the amorphous alloy ribbon or the like at the holding temperature can be set to 0 to 60 minutes, and depending on the composition of the alloy, it is 0 minutes, that is, the temperature is lowered immediately after the temperature is raised and the holding time is kept. Even without it, the desired effect can be obtained. Further, even if the holding time is longer than 60 minutes, the magnetic characteristics are not improved, the manufacturing time becomes long, and the productivity deteriorates, which is not preferable. Further, particularly in the case of a composition not containing Si, the desired effect can be obtained even if the holding time is 10 minutes or less. This is because when Si is added, F
This is because it is necessary to sufficiently dissolve Si in e and elongate the holding time.

[0039]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. (Preparation of sample) Fe ₈₄ Nb _6.95 Nd _0.05 B ₉ composition,
Fe ₈₃ Nb _6.9 Nd _0.1 B ₉ composition, Fe ₈₄ Nb _6.8 Nd
_0.2 B ₉ composition, Fe ₈₄ Nb _6.6 Nd _0.4 B ₉ composition,
The raw materials were adjusted so as to have a composition of Fe ₈₃ Nb _6.9 MN _0.1 B ₉ (MN is Misch metal) and a composition of Fe ₈₄ Nb _6.8 MN _0.2 B ₉ (MN is Misch metal), and they are arranged in an Ar gas atmosphere. They are individually high-frequency melted, and the melted raw materials are respectively poured into a mold to obtain a master alloy of each composition.
About 20 μm thick and about 20 μm wide by using a liquid quenching method in which the master alloy is subjected to high-frequency melting in a nozzle in an Ar gas atmosphere, and the molten metal is blown out from the nozzle onto a copper roll rotating at high speed to quench the melt. Multiple alloy ribbon samples of 15 mm were obtained. Next, these thin ribbons were cut into an outer diameter of 10 mm and an inner diameter of 6
A sample (sample of the example) was obtained by mechanically punching into a circular ring of mm and heat treatment. The heat treatment condition is a heating rate of 18
0 ° C / min, heat treatment temperature 625 ° C (898K) to 7
The temperature was maintained at 25 ° C. (998 K) for 5 minutes, and the temperature decreasing rate (cooling rate) was 180 ° C./minute. [Comparative Example] Further, a sample (Comparative Example sample) was obtained in the same manner as described above, except that a raw material adjusted to have a composition of Fe ₈₄ Nb ₇ B ₉ was used for comparison.

[Measurement] The magnetic permeability (μ ′), the saturation magnetic flux density (B ₁₀ ) and the saturation magnetic field (Br) at 10 kHz and 400 A / m (5 mOe) of each of the samples obtained in the comparative example and the example were measured. The heat treatment temperature dependence of the coercive force (Hc) was measured. The results are shown in Tables 1 to 7.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

[0044]

[Table 4]

[0045]

[Table 5]

[0046]

[Table 6]

[0047]

[Table 7]

As is clear from the results shown in the comparative examples of Table 1 and the example samples of Tables 2 to 7, a trace amount (0.05 atomic%) of Nd was added to the sample having the composition of Fe ₈₄ Nb ₇ B _9. The sample added and annealed at an appropriate temperature of 650 ° C. to 700 ° C. was able to enhance the coercive force without lowering the saturation magnetic flux density. Further, it is possible to obtain the effect that the magnetic permeability can be improved without causing a decrease in the saturation magnetic flux density until the added amount of Nd reaches 0.4 atomic%. In addition, Fe ₈₄ N
b ₇ was added to the sample of B ₉ having a composition of trace misch metal (0.1 atomic% to 0.2 atomic%) (MN), proper 65
The sample annealed at 0 ° C. to 700 ° C. could increase the coercive force without decreasing the saturation magnetic flux density. Further, it is possible to obtain the effect that the magnetic permeability can be improved without causing a decrease in the saturation magnetic flux density until the amount of misch metal added reaches 0.2 atomic%. Also, Fe
A sample having a composition of ₈₄ Nb ₇ B ₉ has a trace amount (0.1 atom% to 0.1%).
In the case of adding 2 atom% of misch metal (MN), since inexpensive misch metal is used, Fe
_The cost can be lower than that of a sample having a composition of ₈₄ Nb ₇ B _{9 to} which Nd is added as a rare earth element. Next, in a comparative sample having a composition of Fe ₈₄ Nb ₇ B ₉ , an amorphous alloy can be obtained by setting the temperature of the molten metal to 1180 ° C., while the Nd-added compositions shown in Tables 2 to 5 are obtained. In the samples of No. 1 and the samples having the misch metal addition composition shown in Tables 6 to 7, 1210 ° C., 1210 ° C.
An amorphous alloy could be obtained even if injection was performed at a high temperature of 220 ° C. (1190 ° C. to 1220 ° C.). Generally, if the injection temperature (blowing temperature) is high, the crystalline phase is likely to precipitate in the ribbon, but the addition of Nd or misch metal relatively stabilizes the amorphous phase. this is,
It is considered that the amorphous forming ability was improved by adding Nd or misch metal.

Next, the results of examining the dependence of the amount of Nd addition on the effective magnetic permeability (μ) at 1 kHz, the coercive force (Hc), and the magnetostriction (λs) of the sample composed of the alloy ribbon having the above composition are shown. As shown in FIG. From the results shown in FIG. 1, it is clear that the magnetic permeability is improved by the addition of Nd, and the coercive force is decreased by the addition of Nd. Further, it is clear that the magnetostriction can be slightly adjusted to the negative side, which is lower than 0, by adding Nd,
It is apparent that the compressive stress at the time of curing the resin to be coated can be adjusted to cancel it.

In FIG. 2, the sample having the above composition is annealed.
Is the starting temperature at which bccFe begins to precipitate when_x1
And T, which is the starting temperature at which other crystalline phases begin to precipitate_x2And D
Measured by TA (Differential Thermal Analyzer)
The results are shown below. When the amount of Nd added is 0, T_x1-T_x2= 28
While the temperature is 3 ° C, the amount of Nd added is 0.2 atom%.
T_x1-T_x2= 288 ℃, Nd addition amount 0.4 atom% smell
T_x1-T_x2= 294 ° C, which is low due to the addition of Nd.
T of at least 288 ° C_x1-T _x2Revealed that
Or it becomes. This temperature difference becomes wider as the amount of Nd added increases.
I tend to go up. In this way, bccFe begins to precipitate
Then, other compound phases (F that adversely affects the soft magnetic properties
e₃There is a large difference in the temperature at which compounds such as B) start to precipitate.
And the precipitation ratio of the compound phase is small, the precipitation ratio of bccFe
Therefore, it is preferable in terms of improving soft magnetic characteristics.
Good Even if the Nb and B concentrations in the alloy are changed, T_x1-T_x2
The value of changes. To achieve relatively good soft magnetic characteristics
To T_x1-T_x2≧ 250 ° C., preferably before
As shown in the above, when Nd is added, T_x1-T_x2Has a wide value
This condition tends to be satisfied because it tends to increase.

Next, FIG. 3 shows the results of examining the structure of the free surface (the surface not in contact with the copper roll) before heat treatment of the samples having the respective compositions by the X-ray diffraction method, and FIG. The results obtained by investigating the structure of the free surface of the alloy ribbon (the surface not in contact with the copper roll) after the heat treatment by the X-ray diffraction method are shown in FIG. From FIG. 3, a halo diffraction pattern peculiar to amorphous is observed in the quenched state, and a unique diffraction pattern is observed in body-centered cubic crystal after the heat treatment. From FIG. 4, the structure of the alloy is From the amorphous phase to the amorphous phase, the bcc phase (b
It can be seen that cc-Fe) has changed to a precipitated one.
In addition, no precipitation of Nd compound crystals was observed in the sample after the heat treatment, and Nd is unlikely to form a solid solution in bccFe.
It is considered that Nd remains in the amorphous phase. Figure 5
The saturation magnetic flux density (B ₁₀ ) of the alloy ribbon sample having the composition of Fe ₈₄ Nb _7-x Nd _x B ₉ shown in Table 1 and 10 kHz, 400
The results of examining the magnetic permeability (μ ') at A / m (5 mOe) and the dependency of coercive force (Hc) on the amount of Nd added are shown below. From the results shown in FIG. 5, in this sample composition, from the viewpoint of soft magnetic characteristics, the sample containing 0.1 to 0.2 atomic% of Nd is excellent, and the optimum heat treatment temperature is 625 to 625.
It is clear that it is in the range of 700 ° C, more preferably 675 to 700 ° C. FIG. 6 shows Fe ₈₄ Nb _6-x Nd _x B ₁₁
Saturation magnetic flux density (B ₁₀ ) of alloy ribbon samples of the following composition and 10
The results obtained by examining the magnetic permeability (μ ') at 400 A / m (5 mOe) and the coercive force (Hc) dependency on the amount of Nd added are shown below. From the results shown in FIG. 6, in this sample composition, N
It is clear that the sample to which d is added in an amount of 0.05 to 0.1 atomic% is excellent, and the optimum heat treatment temperature is in the range of 550 to 650 ° C, more preferably in the range of 600 to 625 ° C.

Next, with respect to the alloy sample having the composition of Fe ₈₄ Nb _7-x Nd _x B ₉ , the state of the ribbon immediately after the liquid was rapidly cooled was examined when x was changed to 0.05 to 0.8 at%. The results are shown in Table 8 below.

[0053]

[Table 8]

From Table 8, the amount of Nd added is 0.05 to 0.5.
Amorphous single phase is obtained in atomic%, but 0.6 atomic%
It can be seen that, when the temperature exceeds 1.0, the compound phase is precipitated in the structure immediately after the liquid is rapidly cooled, and becomes a mixed phase of the amorphous phase and the compound phase. If the compound phase precipitates immediately after the liquid is rapidly cooled, it becomes difficult to obtain a uniform crystal structure after heat treatment, and the soft magnetic properties deteriorate, resulting in 100
It becomes difficult to obtain an effective magnetic permeability of 1 kHz after heat treatment of 00 or more. Therefore, in the present invention, it is understood that the addition amount of the element Q is preferably 0.5 atomic% or less.

Next, referring to FIG. 7, Fe ₈₄ Nb _7-x Nd _x B ₉ (X
Is 0, 0.2, 0.4, or 0.5) of each composition alloy sample, the structure immediately after rapid cooling of the free surface (the surface not in contact with the copper roll) was analyzed by X-ray diffraction method. Regarding the results of the examination, the results obtained by improving the resolution of the measuring device and measuring again more finely than the state shown in FIG. 3 are shown. From FIGS. 3 and 7, the halo diffraction pattern peculiar to the amorphous material was clearly recognized in the sample at any of X = 0, 0.2 and 0.4 immediately after the rapid cooling. Further, in any of the samples with X = 0.2, 0.4, and 0.5, a peak that is considered to be Fe ₃ B is included in a part of the halo diffraction pattern that appears near 2θ = 52 °. It was found that the Fe ₃ B was partially precipitated. In addition, a small peak, which is considered to be bccFe (200), was observed in the vicinity of 2θ = 76 to 78 ° in both samples of X = 0.4 and 0.5. Further, in the sample of X = 0.5, a bccFe (110) peak was also observed near 2θ = 52 °.

FIG. 8 shows a composition alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.1, 0.2,
It is a figure which shows the DSC curve of the composition alloy of the Example which is any of 0.3, 0.4, and 0.5. The DSC curve shown in FIG. 8 is known to be capable of accurately measuring the crystallization temperature, and the crystallization temperature can be measured more accurately than the result by the DTA shown in FIG. From the results shown in FIG. 8, it is clear that the crystallization temperature Tx is exhibited in any composition, and the addition amount of Nd as a rare earth element is increased in the range of 0.1 to 0.5 atomic%. As a result, it can be seen that the crystallization temperature Tx is slightly lowered. This decrease in Tx suggests that the formation of crystal nuclei is caused from a low temperature, and it is expected that microcrystallization is accelerated.

FIG. 9 shows a composition alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.05, 0.02).
Saturation magnetic flux density (Bs: T) and magnetic permeability (μ: 1 KHz: of an alloy having a composition of 1, 0.2, 0.4, or 0.5)
It is a figure which shows the measurement result of x10 < ⁴ >) and coercive force (Hc: A / m). The measurement conditions are the same as in the case of the sample shown in FIG. In the measurement results of FIG. 9, a part of the measurement results of the magnetic permeability μ and the coercive force Hc is the same as the measurement result shown in FIG. 1, but in FIG. 9, Nd is 0.5 atom in the magnetic permeability and the coercive force. It is the result of adding the measurement result when it is set to%. In addition,
I tried to make multiple samples containing Nd in an amount of more than 0.5 atomic% and 0.6 atomic%. However, some of the thin ribbon samples were destroyed during quenching from the molten metal, making it impossible to manufacture. there were. From the above, it was found that when Nd is contained in excess of 0.5 atomic%, the yield of ribbon production is likely to decrease.

From the measurement results shown in FIG. 9, when Nd as a rare earth element is added to the FeNbB system, 0.05
The saturation magnetic flux density does not change at all even if it is added in the range of 0.5 to 0.5 atomic%, and maintains a good value, and the saturation magnetic flux density is 0.05 to 0.4.
Addition in the range of atomic% does not cause any problem in terms of soft magnetic properties, but it is clear that the addition of 0.5 atomic% lowers the magnetic permeability and increases the coercive force. From the viewpoint of coercive force, the coercive force of the sample containing 0.1 atom% is slightly lower than that of the sample containing 0.05 atom% of Nd. In view of the above, the most preferable range of the rare earth element content is 0.1 atom% or more and 0.4 atom% or less.

Next, Fe ₈₄ containing no rare earth element added
The composition of the comparative example Nb ₇ B ₉ and the composition of this comparative example are Nb 7
Nd in the form of substitution with 0.03 atomic%, 0.05 atomic%,
Fe added with 0.1 atom%, 0.2 atom%, 0.4 atom%
FIG. 10 shows the results obtained by measuring the Curie temperature immediately after rapid cooling of these amorphous alloy ribbons by making alloy ribbons from the molten alloy having the composition of ₈₄ Nb _7-X Nd _X B ₉ by the liquid quenching method.
Shown in. In FIG. 10, the measured value represented by RQ6 is a master alloy prepared by high frequency melting in an Ar atmosphere.
The measurement result of the sample which manufactured the alloy ribbon by liquid quenching from this mother alloy is shown, and the measured value of what is denoted as RQ8 is the mother alloy prepared by arc melting in the atmospheric pressure, and liquid quenching from this mother alloy. The measurement result of the sample which manufactured the alloy ribbon is shown. In the above measurement, the magnetic permeability could not be accurately measured because the conductor wire used for the strand was long in order to heat the core. There is a large difference in the magnetic permeability between the sample of X = 0.05 atomic% and the sample of X = 0.2 atomic% in FIG. 10 because the length of the conductive wire is different between these samples. In addition, in the measured values of each sample represented by RQ6 and RQ8 in FIG. 10, the value of μ on the vertical axis is a value measured by winding the thin ribbon in a coil shape and then winding to see the Curie temperature. Since the magnetic permeability changes according to the length of the line,
The magnetic permeability shown in is not the intrinsic magnetic permeability inherent to the material.

From the result shown in RQ8 of FIG.
Fe₈₄Nb₇B₉Curie temperature of amorphous alloy ribbons of different composition
The temperature was 12 ° C, and Nd as a rare earth element was added.
Fe ₈₄Nb_6.9Nd_0.1B₉Amorphous alloy ribbon of composition
Curie temperature was found to be 21 ° C and Nd was added
The Curie temperature of the prepared sample is the Curie temperature of the composition of the comparative example.
You can see that it is much higher. In this way, the liquid
Since the Curie temperature of the amorphous phase immediately after cooling rises,
Curie temperature of residual amorphous phase after heat treatment should also rise
Is predicted. The Curie temperature of this residual amorphous phase rises
By doing so, the magnetization of the residual amorphous phase may also increase.
It is conceivable that the magnetism of bccFe, which is the crystalline phase, between the fine crystal grains
The mechanical bond becomes stronger, and the soft magnetic characteristics of the alloy itself
As a result of the improved magnetic properties, as shown in FIG. 1 and FIG.
Is considered to have improved. The rare earth element to be added
The amount of Nd as a base is 0.03 atomic%, 0.05 atomic%,
Change like 0.1 atom%, 0.2 atom%, 0.4 atom%
The Curie temperature changes depending on the amount added.
Both, RQ6 and RQ even under the conditions for producing the master alloy
It was revealed that the sample No. 8 was slightly different.

As described above, the Curie temperature is changed by adding Nd by Nb substitution. Nd addition effect 1
One example is that the Curie temperature can be raised in this way, but the Curie temperature in the amorphous state is 0.
℃ ~ 100 ℃ range (0 ℃ or more, 100 ℃ or less range)
Is desirable. If it is less than 0 ° C, the Curie temperature of the residual amorphous phase after heat treatment is also low, and sufficient soft magnetic characteristics cannot be obtained. Further, when the temperature is 100 ° C. or higher, the Fe concentration is low, and sufficient saturation magnetization cannot be obtained. In order to balance high saturation magnetization and magnetic permeability at a high level, the Curie temperature is more preferably 15 to 50 ° C. From this requirement, as shown in the measurement results in the lower part of FIG. 10, when the Nd concentration dependence of the Curie temperature of the samples of RQ6 and RQ8 is seen, the Curie temperature rises when the amount of Nd added is increased. It became clear that there was a tendency.

FIG. 11 shows a composition alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.1, 0.1).
It is a figure which shows the measurement result of the X-ray-diffraction peak after the optimal annealing of the alloy of the composition of either 4 or 0.5). Figure 11
From the results shown in, the peak of bccFe near 2θ = 52 °, the peak of bccFe at 2θ = 76 to 78 °, 2θ =
In addition to the bccFe peak at 95 to 100 °,
2θ = 85-9 in a sample with Nd addition amount of 0.5 atomic%
An unknown peak occurs near 0 °, and from this result, it can be presumed that it is a sign that some compound phase begins to precipitate and the magnetic properties start to deteriorate at a rare earth addition amount of 0.5 atom%.

FIG. 12 shows a composition alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.05, 0.0.
Crystal grain size (D / nm) and magnetostriction (λs) after optimal annealing of an alloy having a composition of 1, 0.2, 0.4, or 0.5)
It is a figure which shows the relationship of / 10 ^<-6 >. Judging from the crystal grain size, the sample with 0.1 atom% is the smallest, but 0.05 atom%
The sample has a small crystal grain size. From the viewpoint of crystal grain size, it seems that the content of the rare earth element is preferably 0.05 atomic% or more.

FIG. 13 shows a test of Nd and other elements as rare earth elements added to the FeNbB system. Fe ₈₄ Nb _6.9 R _0.1 B ₉ (R is Y, La, Ce, P
It is a figure which shows the X-ray-diffraction pattern of the ribbon just after rapid cooling (asQ) of the alloy of composition which is any of r, Nd, and Sm. Figure 1
From the results shown in 3, there is a peak near 2θ = 52 ° which shows precipitation of Fe ₃ B in addition to a broad curve (R is any of Y, La, Ce, and Nd). It can be presumed that the sample has a compound phase, which is considered to be Fe ₃ B, immediately after being rapidly cooled, but has good magnetic properties.

FIG. 14 shows a test of the rare earth elements added to the FeNbB system other than Nd.
e ₈₄ Nb _6.9 R _0.1 B ₉ (R is Gd, Tb, Dy, Ho,
It is a figure which shows the X-ray-diffraction pattern of the ribbon immediately after rapid cooling (asQ) of the alloy of composition which is Er, Tm, or Lu. From the results shown in FIG. 14, there are some peaks showing precipitation of Fe ₃ B in addition to a broad curve near 2θ = 52 ° (R is any of Dy, Er, and Tm). It is presumed that the sample is likely to have a good magnetic property although the compound phase, which is considered to be Fe ₃ B, is likely to precipitate immediately after the rapid cooling.

FIG. 15 shows the magnetic permeability (μ: 1 KHz) and coercive force of an alloy having a composition of Fe ₈₄ Nb _7-X R _X B ₉ (R is Y, La, Ce, Pr, Nd, or Sm). It is a figure which shows (Hc) and crystallization temperature (Tx). Y, La, Ce, Pr, N showing the rare earth elements contained in FIG.
The numerical value 0.1 above the element symbols such as d and Sm indicates that the amount of the contained rare earth element is 0.1 atom%, and the numerical value 0.2 indicates the amount of the contained rare earth element. Is 0.2 at%. Further, FIG. 15 shows the characteristics of the sample having the composition of Fe ₈₄ Nb ₇ B ₉ in which the value indicated by the horizontal chain line does not include the rare earth element. FIG. 16 shows that Fe ₈₄ Nb _7-X R _X B ₉ (R
FIG. 3 is a diagram showing magnetic permeability (μ: 1 KHz), coercive force (Hc), and crystallization temperature (Tx) of an alloy having a composition of Gd, Tb, Dy, Ho, Er, Tm, or Lu). Also,
The value indicated by the horizontal chain line in FIG. 16 is F to which rare earth is not added.
The characteristics of the sample having the composition of e ₈₄ Nb ₇ B ₉ are shown.

From the results shown in FIG. 15 and FIG. 16, La, Ce, Pr, Sm, Gd, T including Y as a rare earth element are included.
Even if any of b, Dy, Ho, Er, Tm, and Lu is contained, it has the same excellent magnetic permeability as the case of Nd described above for the sample having the composition of Fe ₈₄ Nb ₇ B _9. It was revealed that a low coercive force can be obtained. In addition, when the rare earth element is added, it is more than 0.2 at 0.1 atom%.
It was revealed that the inclusion of atomic% tends to lower the crystallization temperature.

FIG. 17 shows Fe ₈₄ Nb _6.5-X La _X B
The magnetic permeability (μ: 1 KHz) and coercive force (H) of an alloy having a composition of _9.5 (X is 0.1, 0.2, 0.3, or 0.4)
It is a figure which shows the annealing temperature dependence of c) and magnetization (Br). When manufacturing a soft magnetic alloy ribbon of these compositions,
The sample is manufactured by liquid quenching in the atmosphere. In the composition system shown in FIG. 17, although the liquid was rapidly cooled in the atmosphere, 650 was obtained in the sample containing 0.2 atomic% of La.
It has been clarified that if the heat treatment is carried out in the range of ° C to 675 ° C, the magnetic permeability of more than 30,000 can be surely obtained. Further, from the characteristics of coercive force and magnetization, the range of 650 to 675 ° C. seems to be the preferable annealing temperature.

FIG. 18 shows Fe _83.5 Nb _6.5-X La _X B
Permeability (μ: 1 KHz), coercive force (Hc), and magnetization (Br) of an alloy having a composition of ₁₀ (X is either 0.1 or 0.2)
FIG. 5 is a diagram showing the annealing temperature dependency of FIG. The measurement result shown in FIG. 18 was similar to the measurement result shown in FIG. FIG. 19
Is the magnetic permeability (μ: 1 KHz), coercive force (Hc) and magnetization (Br) of an alloy having a composition of Fe _84-X La _X Nb _6.5 B _9.5 (X is 0.2 or 0.4). It is a figure which shows annealing temperature dependence. The measurement results shown in FIG. 19 were similar to the measurement results shown in FIGS. 17 and 18.

FIG. 20 shows the free surface of the composition alloy ribbon of Fe ₈₄ Nb ₇ B _{9 of the} comparative example (measured on the surface of the ribbon which is not in contact with the rotating cooling roll), the X-ray diffraction pattern immediately after the rapid cooling, and Fe.
A diagram showing the results of the X-ray diffraction patterns immediately after rapid cooling (measured on the surface of the ribbon that does not come into contact with the rotating cooling roll) of the alloy ribbon having the composition of ₈₄ Nb _6.9 La _0.1 B ₉ after changing the production atmosphere. Is. In the alloy ribbon sample of the composition of the comparative example of Fe ₈₄ Nb ₇ B _9, when the atmosphere of Ar atmospheric pressure is changed to the Ar depressurized atmosphere, the peak of bcc (200) becomes strong, whereas the Fe ₈₄ Nb _6.9 La _0.1 In the alloy ribbon sample having the composition B _9, a strong peak of bcc (200) is not observed in both the atmosphere of Ar atmospheric pressure and the reduced pressure atmosphere of Ar. When the atmospheric pressure atmosphere of Ar is changed to the depressurized atmosphere of Ar, it is difficult to smoothly conduct heat during rapid solidification because the amount of gas existing in the atmosphere is small, and as a manufacturing condition, rapid cooling tends to be difficult.

FIG. 21 shows the magnetic permeability and coercive force of the alloy ribbon of the composition of Fe ₈₄ Nb ₇ B _{9 of the} comparative example and the alloy ribbon of the composition of Fe ₈₄ Nb _6.9 La _0.1 B ₉ of Ar during rapid cooling. It is a figure which shows atmospheric pressure dependence. The RQ atmosphere pressure on the horizontal axis of FIG. 21 represents Ar gas pressure, and the case of 0 represents Ar gas atmospheric pressure atmosphere, and shows that the atmosphere becomes more decompressed as the value of − (minus) increases. The decrease in Ar gas pressure means that the amount of gas present in the quenching atmosphere decreases, so when the molten metal is jetted onto a rotating cooling roll to produce a ribbon by the quenching method. It means that heat is taken from the ribbon by heat conduction, that is, the cooling capacity is lowered. Thus Fe ₈₄ than the magnetic properties of the prepared Fe ₈₄ Nb ₇ alloy ribbon of the composition of B ₉ becomes Comparative Example in a reduced pressure atmosphere such as -40CmHg Nb
_{From the fact that} the alloy ribbon having the composition of _6.9 La _0.1 B ₉ is superior in the magnetic properties, it is considered that the alloy of the composition system containing the rare earth is advantageous for the production even in the reduced pressure atmosphere.

[0072]

As described above, according to the present invention,
(Fe or Fe-Z) -BM alloy or (Fe or Fe-Z) -BMMT alloy with one or more elements Q of rare earth elements including Y. By adding, it is possible to realize high magnetic permeability while maintaining high saturation magnetic flux density. Since the element Q is an element having an amorphous forming ability and is an element which is not solid-dissolved in Fe, it easily produces nuclei of fine crystals and has an effect of reducing the crystal grain size after heat treatment. . Further, in the case of manufacturing by the liquid quenching method, since it is possible to increase the temperature of the molten metal blown out by adding the element Q, it is possible to reduce the viscosity of the molten metal at the time of blowing out, without clogging the nozzle, It is possible to obtain a high-quality amorphous alloy ribbon without precipitation of a compound phase, and on the basis of this, an Fe-based soft magnetic alloy having excellent soft magnetic properties can be obtained.

The element Q is (Fe or Fe-
Z) -BM system alloy or (Fe or Fe-Z) -B
Since the improvement of the soft magnetic properties is caused by adding a small amount to the -MT alloy, Fe and Co in the soft magnetic alloy are added.
Since the decrease in the concentration of Ni and Ni is small, the saturation magnetic flux density can be kept high. Further, since the element Q is an element having an amorphous forming ability, the addition amount of B and M can be reduced by adding the element Q, so that the Fe concentration becomes relatively high, so that a high saturation magnetic flux is obtained. Density is possible. It is because the element Q is bcc containing Fe as a main component.
Since it does not form a solid solution in the phase (body-centered cubic phase) and remains in the amorphous phase, it does not become an impurity, and also serves the same function as B or M. Therefore, the amount of B or M added Because it can be reduced. Further, since the element Q can raise the Curie temperature of the residual amorphous phase, the soft magnetic characteristics can be improved. Further, in the Fe-based soft magnetic alloy of the present invention, in which Mb in the composition formula contains Nb, the effect of reducing the growth rate of fine crystal nuclei and the ability to form an amorphous state are obtained. While keeping it, it is possible to prevent oxidation relatively, and the cost can be kept low.

[Brief description of drawings]

FIG. 1 is a graph showing the results of examining the heat treatment temperature dependence of effective magnetic permeability (μ), coercive force, and magnetostriction (λs) of an alloy sample having a composition of Fe ₈₄ Nb _7-x Nd _x B _9. Is.

FIG. 2 is a graph showing precipitation temperatures of bccFe and other compound phase precipitation temperatures of alloy ribbon samples having a composition of Fe ₈₄ Nb _7-x Nd _x B ₉ .

FIG. 3 is a free surface of an alloy ribbon having a composition of Fe ₈₄ Nb _7-x Nd _x B ₉ (a surface not in contact with a copper roll).
3 is a graph showing an X-ray diffraction pattern of the structure before the heat treatment of FIG.

FIG. 4 is a free surface of an alloy ribbon having a composition of Fe ₈₄ Nb _7-x Nd _x B ₉ (a surface not in contact with a copper roll).
4 is a graph showing an X-ray diffraction pattern of the structure after the heat treatment of FIG.

FIG. 5 is a graph showing the saturation magnetic flux density (B ₁₀ ), the effective magnetic permeability (μ ′) and the coercive force (Hc) of an alloy ribbon sample having a composition of Fe ₈₄ Nb _7-x Nd _x B _9. It is a graph which shows temperature dependence and Nb addition amount dependence.

FIG. 6 is a graph showing the saturation magnetic flux density (B ₁₀ ), the effective magnetic permeability (μ ′) and the coercive force (Hc) of an alloy ribbon sample having a composition of Fe ₈₄ Nb _7-x Nd _x B _11. It is a graph which shows temperature dependence and Nb addition amount dependence.

FIG. 3 shows that Fe ₈₄ Nb _7-x Nd _x B ₉ (X is 0,
A graph showing the result of re-measurement of the X-ray diffraction pattern immediately after rapid cooling of the free surface of the alloy ribbon having a composition of 0.2, 0.4, or 0.5) while improving the resolution of the measuring instrument. is there.

FIG. 8 is a compositional alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _{7- X} Nd _X B ₉ (X is 0.1, 0.2, 0.2).
It is a figure which shows the DSC curve of the composition alloy of the Example which is any of 3, 0.4, and 0.5).

9 is a compositional alloy of Fe ₈₄ Nb ₇ B _{9 of} a comparative example, and Fe ₈₄ Nb _{7- X} Nd _X B ₉ (X is 0.05, 0.1,
It is a figure which shows the measurement result of saturation magnetic flux density (Bs), magnetic permeability ((mu): 1kHz), and coercive force (Hc) of the composition alloy of the Example which is any of 0.2, 0.4, and 0.5. .

FIG. 10 is a compositional alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.03, 0.02).
05, 0.1, 0.2, or 0.4) alloys having a composition of each of which is formed by a liquid quenching method, and the Curie temperature of these amorphous alloy ribbons is determined by a coil. The results obtained by changing the number of turns of the alloy and the relationship between the alloy composition and the Curie temperature are shown.

FIG. 11 is a compositional alloy of Fe ₈₄ Nb ₇ B ₉ and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.1, 0.1).
It is a figure which shows the measurement result of the X-ray-diffraction peak after the optimal annealing of the alloy of the composition of either 4 or 0.5).

FIG. 12 is a composition alloy of Fe ₈₄ Nb ₇ B _{9 as} a comparative example and Fe ₈₄ Nb _7-X Nd _X B ₉ (X is 0.05, 0.02).
It is a figure which shows the crystal grain size and the magnetostriction after optimal annealing of the alloy of the composition which is 1, 0.2, 0.4, or 0.5).

FIG. 13 is an X-ray diffraction pattern of a ribbon immediately after quenching (asQ) of an alloy having a composition of Fe ₈₄ Nb _6.9 R _0.1 B ₉ (R is Y, La, Ce, Pr, Nd, or Sm). It is a figure which shows a figure.

FIG. 14 shows X of ribbons immediately after quenching (asQ) of an alloy having a composition of Fe ₈₄ Nb _6.9 R _0.1 B ₉ (R is any of Gd, Tb, Dy, Ho, Er, Tm, and Lu). It is a figure which shows a line diffraction pattern.

FIG. 15 is a graph showing the magnetic permeability (μ: 1 KHz) and retention of an alloy having a composition of Fe ₈₄ Nb _7-X R _X B ₉ (R is any of Y, La, Ce, Pr, Nd, and Sm). It is a figure which shows magnetic force (Hc) and crystallization temperature (Tx).

FIG. 16 shows that Fe ₈₄ Nb _7-X R _X B ₉ (R is G
d, Tb, Dy, Ho, Er, Tm, or Lu)
Permeability (μ: 1KHz) and coercive force (H
It is a figure which shows c) and crystallization temperature (Tx).

FIG. 17 shows that Fe ₈₄ Nb _6.5-X La _X B
The magnetic permeability (μ: 1 KHz) and coercive force (H) of an alloy having a composition of _9.5 (X is 0.1, 0.2, 0.3, or 0.4)
It is a figure which shows the annealing temperature dependence of c) and magnetization (Br).

FIG. 18 shows Fe _83.5 Nb _6.5-X La _X B
Permeability (μ: 1 KHz), coercive force (Hc), and magnetization (Br) of an alloy having a composition of ₁₀ (X is either 0.1 or 0.2)
FIG. 5 is a diagram showing the annealing temperature dependency of FIG.

FIG. 19 shows Fe _84-X La _X Nb _6.5 B
The magnetic permeability (μ: 1 KHz), coercive force (Hc), and magnetization (B) of an alloy having a composition of _9.5 (X is 0.2 or 0.4)
It is a figure which shows the annealing temperature dependence of r).

FIG. 20 is an X-ray diffraction pattern immediately after rapid cooling of a comparative composition alloy ribbon of Fe ₈₄ Nb ₇ B ₉ and Fe ₈₄ Nb _6.9.
The X-ray diffraction pattern immediately after quenching of the alloy strip la _0.1 B ₉ having a composition by changing the respective production atmosphere is a graph showing the results obtained.

FIG. 21 is a graph showing the magnetic permeability and coercive force of Fe ₈₄ Nb ₇ B _{9 as} a comparative alloy and Fe ₈₄ Nb _6.9 La _0.1 B _{9 as} a function of Ar atmosphere pressure during quenching. FIG.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Yamamoto             1-7 Aki, Otsuka-cho, Yukiya, Ota-ku, Tokyo             Su Electric Co., Ltd. F term (reference) 5E041 AA11 CA01 CA02 CA05 NN01                       NN14 NN18

Claims (18)

[Claims] 1. An Fe-based soft magnetic alloy represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y Q z however Z is Ni, 1 kind or two elements of Co, M
Is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W, and Q is one or more elements selected from rare earth elements including Y. Yes,
The composition ratios a, b, x, y, and z are 0 ≦ a ≦ 0.2,
75 atom% ≦ b ≦ 93 atom%, 0.5 atom% ≦ x ≦ 18
Atomic%, 4 atomic% ≦ y ≦ 9 atomic% and 0 <z ≦ 0.5 atomic%. 2. An Fe-based soft magnetic alloy represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y Q z X t However, Z is Ni, 1 kind or two elements of Co,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W, and Q is one or more elements of rare earth elements including Y. , X is one or more elements selected from Si, Al, Ge, Ga, P, C and Cu, and a, b, x, which indicate the composition ratio,
y, z and t are 0 ≦ a ≦ 0.2 and 75 atomic% ≦ b ≦ 93
Atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y
≦ 9 atomic%, 0 <z ≦ 0.5 atomic%, 0 <t ≦ 5 atomic%
Is. 3. The Fe-based soft magnetic alloy according to claim 1, wherein the M contains at least one of Nb, V, Mo, and W. 4. The Fe-based soft magnetic alloy according to claim 1, wherein M in the composition formula contains Nb. 5. Q in the composition formula is Y, La, Ce,
The Fe-based soft magnetic alloy according to any one of claims 1 to 4, which contains at least one of Pr, Nd, Dy, and Tb. 6. Q in the composition formula is Pr, Nd, D
The Fe-based soft magnetic alloy according to claim 1, containing at least one of y and Tb. 7. The Fe-based soft magnetic alloy according to claim 1, wherein Q in the composition formula contains at least one of La and Ce. 8. The Fe-based soft magnetic alloy according to claim 1, wherein Q in the composition formula is misch metal or contains misch metal. 9. The Fe-based soft magnetic alloy has a total structure of 50
%, And bccFe mainly composed of fine crystal grains having an average crystal size of 30 nm or less, the remainder being an amorphous phase, and b
The temperature difference between the start temperature T _{x1 at} which the ccFe crystal phase is precipitated and the start temperature T _x2 at which the crystal phase other than the bccFe crystal grains is precipitated is 2
It is 50 degreeC or more, Fe-based soft magnetic alloy in any one of Claims 1-8 characterized by the above-mentioned. 10. The Fe group according to claim 1, wherein a temperature difference between the temperature T _x1 and a temperature T _{x2 at} which a crystal phase other than the bccFe crystal grains is precipitated is 285 ° C. or more. Soft magnetic alloy. 11. The t indicating the composition ratio of the element X is 0.1.
The Fe-based soft magnetic alloy according to any one of claims 1 to 9, wherein the range is atomic% ≤ t ≤ 5 atomic%. 12. The t indicating the composition ratio of the element X is not more than 0.1.
The Fe-based soft magnetic alloy according to any one of claims 1 to 10, wherein 1 atomic% ≤ t ≤ 1 atomic% is set. 13. The z indicating the composition ratio of the element Q is 0.1.
The Fe-based soft magnetic alloy according to any one of claims 1 to 12, characterized in that the content is in the range of 01 atom% ≤ t ≤ 0.4 atom%. 14. The z showing the composition ratio of the element Q in atomic%.
Is in the range of 0.05 atomic% ≤ t ≤ 0.1 atomic%, Fe according to any one of claims 1 to 12,
Base soft magnetic alloy. 15. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy is heat-treated, and the Curie temperature before the heat-treatment is in the range of 0 to 100 ° C. Base soft magnetic alloy. 16. The Fe-based soft magnetic alloy according to claim 1, wherein the effective magnetic permeability of the Fe-based soft magnetic alloy at 1 kHz is 30,000 or more. 17. The Fe-based soft magnetic alloy according to claim 1, wherein the saturation magnetization of the Fe-based soft magnetic alloy is 1.5 T or more. 18. BccFe mainly composed of fine crystal grains having an average crystal grain size of 30 nm or less, the balance being an amorphous phase, and a temperature T _x1 at which the bccFe crystal phase is precipitated and bccFe.
The temperature difference of the temperature T _{x2 at} which the crystal phase other than the crystal grains precipitates is 25
An Fe-based soft magnetic alloy characterized by being set at 0 ° C.