JP2000160241A - PRODUCTION OF Fe BASE SOFT MAGNETIC ALLOY - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an Fe base soft magnetic alloy improved in soft magnetic properties, small in the change with lapse of time of magnetic properties even if being left standing for long hours under high temperature, capable of corresponding to working at the time of producing a transformer or the like and preferable as a transformer or the like. SOLUTION: In this method for producing an Fe base soft magnetic alloy, an amorphous alloy essentially consisting of Fe and contg. one or >= two kinds of elements M selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W and Mn and B is formed into a fine crystal alloy with a fine bcc structure of <=30 nm average crystal grain size essentially consisting of the crystal grains of Fe and contg. amorphous phases by 1st heat treatment, which is thereafter subjected to 2nd heat treatment at the holding temp. of 100 deg.C to the one equal to or below the holding temp. in the 1st heat treating temp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an Fe-based soft magnetic alloy used for a magnetic head, a transformer, a choke coil, and the like. The present invention relates to a method for producing an Fe-based soft magnetic alloy in which the magnetic properties change little with time even if left for a long time.

[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. Easy to obtain thin shape. Also,
The magnetic head is required to have the following characteristics in addition to the characteristics described in (1) to (4) due to restrictions in the manufacturing process. High corrosion resistance.

Therefore, when producing a soft magnetic alloy or a magnetic head, material research is being conducted on various alloy systems from these viewpoints. Conventionally, for the aforementioned applications,
Crystalline alloys such as Sendust, Permalloy, and silicon steel are used, and recently, Fe-based and Co-based amorphous alloys have also been used.

[0004]

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 higher coercive force of a magnetic recording medium accompanying a higher recording density. Further, in the case of a transformer or a choke coil, further miniaturization is required in accordance with the miniaturization of electronic equipment, and thus a magnetic material having higher performance is desired.
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). However, silicon steel has a drawback of as low as about 0.8 T, and silicon steel has a drawback that the saturation magnetic flux density is high but 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. Further, the thermal stability of the amorphous alloy is not sufficient, and there are still unsolved aspects. As described above, it is difficult to combine high saturation magnetic flux density with excellent soft magnetic characteristics.

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

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

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

As a method for producing these Fe-based soft magnetic alloys, for example, as described in Japanese Patent Application Laid-Open No. Hei 3-21909, rapid cooling is performed by spraying a molten alloy onto a high-speed rotating cooling body. The soft magnetic alloy ribbon obtained in this manner is subjected to a heat treatment for maintaining the ribbon at a temperature not lower than the crystallization temperature of the metal for about 1 hour, so that a crystal phase is formed in the soft magnetic alloy which was amorphous when quenched. As a result, a soft magnetic alloy exhibiting excellent soft magnetic properties having high saturation magnetic flux density and magnetic permeability, having high hardness and excellent heat resistance can be obtained. By the way, when the soft magnetic alloy is used as a transformer or the like, it must be left in a heated state for a long time at the time of processing at the time of manufacturing. However, the soft magnetic alloy manufactured as described above is in a heated state (high temperature state). ), There is a problem that the magnetic properties change greatly with time if left for a long time. Further, when the soft magnetic alloy is used in small electronic devices, for example, magnetic heads, if the steady detection current is increased to further improve the output, the magnetic head will reach a high temperature exceeding about 200 ° C. If the soft magnetic alloy is used for a long time at a high temperature, the magnetic properties of the soft magnetic alloy greatly change with time, and there is a problem in the reliability of the obtained product.

According to the present invention, the method of manufacturing a soft magnetic alloy of the above-mentioned patent application is developed to improve the soft magnetic properties, and the magnetic properties are less changed over time even when left for a long time in a high temperature state. It is an object of the present invention to provide a method for producing an Fe-based soft magnetic alloy which is suitable for a transformer, which can cope with the working at the time.

[0011]

According to the present invention, there is provided a method for producing an Fe-based soft magnetic alloy, which comprises Fe as a main component, Ti, Zr, Hf, V, Nb, Ta, Mo,
An amorphous alloy containing one or more elements M and B selected from W and Mn is subjected to a first heat treatment to form fine bcc structure Fe grains having an average grain size of 30 nm or less. After forming a microcrystalline alloy mainly containing an amorphous phase,
As described above, the second heat treatment is performed at a holding temperature equal to or lower than the holding temperature of the first heat treatment temperature.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method of manufacturing an Fe-based soft magnetic alloy, the holding temperature of the second heat treatment is 200-200. It is characterized by 400 ° C. Further, in order to solve the above-mentioned problems, the method for producing an Fe-based soft magnetic alloy according to the present invention is the method for producing an Fe-based soft magnetic alloy described above, wherein the second heat treatment is maintained for 0.5 to 100 hours. It is characterized by performing. In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is the same as the method of manufacturing an Fe-based soft magnetic alloy described above,
Is carried out by holding the heat treatment for 1 to 30 hours.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method of manufacturing an Fe-based soft magnetic alloy,
It is performed at a heating rate of 200 ° C./min.
Further, in order to solve the above-mentioned problem, the method for producing an Fe-based soft magnetic alloy according to the present invention is the same as the above-mentioned method for producing an Fe-based soft magnetic alloy, wherein the holding temperature of the first heat treatment is 500
~ 800 ° C.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method of manufacturing an Fe-based soft magnetic alloy, the Fe-based soft magnetic alloy has the following composition formula: It is characterized by being shown. _{(Fe 1-a Z a)} b B x M y where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn, 0 ≦ a ≦ 0.1, 75 atomic% ≦ b ≦ 93 atomic%,
0.5 at% ≦ x ≦ 18 at%, 4 at% ≦ y ≦ 9 at%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b B x M y X z where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn,
X is Si, Al, Ge, Ga, 0 ≦ a ≦ 0.1,
75 atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18
Atomic%, 4 atomic% ≦ y ≦ 9 atomic%, and z ≦ 5 atomic%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b B x M y T t where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn,
T is 1 selected from Cu, Ag, Au, Pd, and Pt.
A kind or two or more kinds of elements, and 0 ≦ a ≦ 0.1, 75
Atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, and t ≦ 5 atomic%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method of manufacturing an Fe-based soft magnetic alloy, the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b B x M y T t X Z where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo ,
One or more elements selected from W and Mn,
T is 1 selected from Cu, Ag, Au, Pd, and Pt.
Species or two or more elements, X is Si, Al, Ge, Ga
0 ≦ a ≦ 0.1, 75 atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y ≦ 9
Atomic%, t ≦ 5 atomic%, and z ≦ 5 atomic%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the method of manufacturing an Fe-based soft magnetic alloy described above, the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. Fe _b Zr _d Nb _{e B x} where 80 atomic% ≦ b, 5 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d / (d + e) ≦ 2.5 / 6,5 atomic% ≦ x ≦ 12.5 atomic%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b Zr d Nb e B x Zn f where, Z is Co, a or Ni,
a ≦ 0.05, 80 atomic% ≦ b, 1.5 atomic% ≦ d ≦ 2.
5 atomic%, 3.5 atomic% ≦ e ≦ 5.0 atomic%, 5 atomic% ≦
x ≦ 12.5 at%, 0.025 at% ≦ f ≦ 0.2 at%, 5.0 at% ≦ d + e ≦ 7.5 at%, 1.5
/6≦d/(d+e)≦2.5/6.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy is represented by the following composition formula: It may be characterized by being shown. However _{Fe b Zr d Nb e B x} Zn f, 80 atomic% ≦ b, 1.5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦ e ≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 1
2.5 atomic%, 0.025 atomic% ≦ f ≦ 0.2 atomic%, and 5.0 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦
d / (d + e) ≦ 2.5 / 6.

In order to solve the above-mentioned problems, a method for producing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method for producing an Fe-based soft magnetic alloy, the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b Zr d Nb e B x Zn f M 'u where Z is Co, a or Ni,
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, a ≦ 0.05, 80 at%
≦ b, 1.5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦
e ≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.5 atomic%
025 atomic% ≦ f ≦ 0.2 atomic%, u ≦ 5 atomic%
5.0 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d /
(D + e) ≦ 2.5 / 6.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{Fe b Zr d Nb e B x} Zn f M 'u where M' is, Cr, Ru, Rh, is one or more elements selected from among Ir, 80 atomic% ≦ b, 1.
5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦ e ≦ 5.0
Atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.025 atomic% ≦ f ≦ 0.2 atomic%, u ≦ 5 atomic%, and 5.0 atomic% ≦ d + e ≦ 7.5 atomic% 1.5 / 6 ≦ d / (d + e)
≤2.5 / 6.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention includes the method of manufacturing an Fe-based soft magnetic alloy described above, wherein the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. _{(Fe 1-a Z a)} b B x M y Zn f where, Z is Co, a or Ni,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W, and a ≦ 0.
05, 80 atom% ≦ b, 5 atom% ≦ x ≦ 12.5 atom%, 5 atom% ≦ y ≦ 7.5 atom%, 0.025 atom% ≦ f
≦ 0.2 atomic%.

In order to solve the above-mentioned problems, a method of manufacturing an Fe-based soft magnetic alloy according to the present invention is characterized in that, in the above-described method of manufacturing an Fe-based soft magnetic alloy, the Fe-based soft magnetic alloy has the following composition formula: It may be characterized by being shown. Fe _{b B x} M _y Zn _f where, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W
80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic% ≦ f ≦ 0.2
Atomic%.

[0025]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the method for producing an Fe-based soft magnetic alloy according to the present invention will be described in detail with reference to the drawings. In order to produce an Fe-based soft magnetic alloy by the production method of the present invention, first, Fe is a main component, and Ti, Zr, Hf,
An amorphous alloy ribbon is formed by quenching an alloy melt containing elements M and B composed of one or more metal elements selected from the group consisting of V, Nb, Ta, Mo, and W. As a method for producing the alloy ribbon, a known method such as injecting a molten alloy into a moving cooling body such as a cooling roll rotating at a high speed can be used.

Subsequently, a first heat treatment is performed on the formed amorphous alloy ribbon at a holding temperature of 500 to 800 ° C. The rapidly quenched alloy ribbon has a structure mainly composed of amorphous material. When heated and heated, a fine bcc structure having an average crystal grain size of 30 nm or less at a certain temperature or higher (body-centered cubic A microcrystalline phase composed of crystal grains of Fe having the structure (1) is precipitated. In this specification, the temperature at which the microcrystalline phase of Fe having the bcc structure precipitates is referred to as a first crystallization temperature. The first crystallization temperature varies depending on the composition of the alloy.
It is about ° C. When the temperature reaches a temperature higher than the first crystallization temperature, a compound phase (second crystal phase) such as Fe ₃ B, or Fe ₃ Zr, which deteriorates soft magnetic characteristics, when Zr is contained in the alloy. Precipitates. In the present specification, the temperature at which such a compound phase precipitates is referred to as a second crystallization temperature.
This second crystallization temperature varies depending on the composition of the alloy,
It is about 740-810 ° C. Therefore, in the present invention, the holding temperature when the first heat treatment is performed on the amorphous alloy ribbon is in the range of 500 ° C. to 800 ° C., and a microcrystalline phase mainly composed of Fe having a bcc structure is preferably precipitated. In addition, it is preferably set according to the composition of the alloy so that the compound phase is not precipitated.

In the present invention, the time for keeping the amorphous alloy ribbon at the above-mentioned holding temperature can be as short as 20 minutes or less. Even if no holding time is used, a high magnetic permeability can be obtained. Particularly, in the case of a composition not containing Cu and Si, especially Si, a high magnetic permeability can be obtained with a shorter holding time of 10 minutes or less. This is S
This is because, when i is added, Si needs to be sufficiently dissolved in Fe to form a solid solution, so that the holding time must be extended. Here, the holding time may be longer than the above range. However, if the holding time is increased, the magnetic properties are not improved, and the manufacturing time is increased and productivity is deteriorated.
In the first heat treatment, the temperature of the amorphous alloy ribbon is
The rate of temperature rise from room temperature to the above holding temperature is 10
以上 C or more, more preferably 10 to 200 ゜ C / min or less,
More preferably, the temperature is 30 ° C./min or more and 100 ° C./min or less. It is preferable that the heating rate is high because the manufacturing time becomes longer as the heating rate is slow, but it is difficult to increase the heating rate to more than 200 ° C./min due to the performance of the current heating device.

After performing the first heat treatment, the alloy ribbon is cooled to a predetermined temperature by air cooling or the like, and the second heat treatment is performed. Thereafter, the alloy ribbon is cooled to room temperature by air cooling or the like. . In the present invention, such a method of performing the second heat treatment during the cooling after the first heat treatment is called two-step annealing. Here, the predetermined temperature refers to a holding temperature at the time of performing the second heat treatment. The holding temperature of the second heat treatment is 1
The temperature is not less than 00 ° C. and not more than the holding temperature of the first heat treatment, preferably 200 to 400 ° C. If the holding temperature in the second heat treatment is less than 100 ° C., the soft magnetic characteristics cannot be sufficiently improved because there is almost no annealing effect.
If the holding temperature of the second heat treatment is higher than the holding temperature of the first heat treatment, Fe ₃ B or alloy
This is because, when Zr is contained, a compound phase (second crystal phase) such as Fe ₃ Zr, which deteriorates soft magnetic properties, is precipitated.

In the second heat treatment, the time for holding the alloy ribbon at the holding temperature is 0.5 to 100 hours, preferably 1 to 30 hours. The holding time (holding time) at the holding temperature when performing the second heat treatment is 0.
If the time is less than 5 hours, the coercive force is large, and the soft magnetic properties such as the magnetic permeability cannot be sufficiently improved. By making the cooling process of the heat treatment in two stages, the soft magnetic properties can be further improved, and an Fe-based soft magnetic alloy with little change over time in the magnetic properties even when left at a high temperature for a long time can be obtained.

In the first heat treatment, the alloy ribbon may be cooled to room temperature by air cooling or the like, and then the second heat treatment may be performed by increasing the temperature at the predetermined temperature. Here, the second heat treatment performed at a lower temperature than the first heat treatment is referred to as low-temperature annealing. As described above, after the first heat treatment precipitates a crystal phase composed of fine bcc-structure Fe crystal grains having an average crystal grain size of 30 nm or less in the amorphous alloy, low-temperature annealing is performed to improve soft magnetic characteristics. It is possible to obtain an Fe-based soft magnetic alloy which can be further improved and has little change in magnetic properties with time even if left for a long time in a high temperature state.

The heat treatment pattern in the method for producing an Fe-based soft magnetic alloy of the present invention includes the following ones. As a heat treatment pattern in the case of performing the two-step annealing, for example, as shown in the graph of FIG. 1, the temperature of the amorphous alloy ribbon is raised from room temperature to the holding temperature of the first heat treatment, and then the holding temperature range After maintaining the above-mentioned holding time at a constant temperature within the above, the temperature is lowered to the holding temperature of the second heat treatment, and after maintaining the above-mentioned holding time at a constant temperature within the above-mentioned holding temperature range, the alloy ribbon is cooled to room temperature by air cooling or the like. Can be mentioned. As a heat treatment pattern in the case of performing the second heat treatment and then performing the low temperature annealing after the first heat treatment, for example, as shown in the graph of FIG. After the temperature is raised to a predetermined temperature within the above-mentioned holding temperature range, the alloy ribbon is cooled to room temperature by air cooling or the like, and then the alloy ribbon is cooled from room temperature to the second temperature. A pattern in which the temperature is raised to the holding temperature of the heat treatment, the temperature is held at the constant temperature within the holding temperature range, and the holding time is maintained, and then the alloy ribbon is cooled to room temperature by air cooling or the like.

The method for producing an Fe-based soft magnetic alloy according to the present invention comprises:
By subjecting the amorphous alloy ribbon to the first heat treatment as described above, a fine b having an average crystal grain size of 30 nm or less can be obtained without precipitating a compound phase such as Fe ₃ B which deteriorates soft magnetic characteristics.
A microcrystalline alloy mainly composed of Fe crystal grains having a cc structure and containing an amorphous phase is obtained. By forming a structure mainly composed of a crystal phase composed of fine crystal grains and a grain boundary amorphous phase existing at the grain boundary, excellent soft magnetic properties can be exhibited. By subjecting the microcrystalline alloy to a second heat treatment at a holding temperature of 100 ° C. or more and equal to or lower than the holding temperature of the first heat treatment temperature, the alloy has more excellent soft magnetic properties, Even if left for a long time, a Fe-based soft magnetic alloy with little change in magnetic properties with time can be obtained.

The reason why the alloy produced according to the present invention exhibits excellent soft magnetic properties is that the soft magnetic properties deteriorate in the conventional crystalline material due to the fine grain size of the bcc crystal grains precipitated by the first heat treatment. This is considered to be because the crystal magnetic anisotropy, which was considered to be one of the causes, was averaged by the magnetic interaction between the bcc particles, and the apparent crystal magnetic anisotropy became very small. Here, if the average crystal grain size of the main crystal grains is larger than 30 nm, the averaging of the crystal magnetic anisotropy is not sufficient, and the soft magnetic characteristics are undesirably deteriorated. It is also considered that the second heat treatment reduces the residual stress in the sample caused by the first heat treatment.

As such an Fe-based soft magnetic alloy, Fe
With Ti, Zr, Hf, V, Nb, Ta, M
Those containing one or more elements M and B selected from o, W, and Mn are preferable. Or, it is particularly suitable for a soft magnetic alloy having a composition represented by the following formulas. _{(Fe 1-a Z a)} b B x M y (Fe 1-a Z a) b B x M y X Z (Fe 1-a Z a) b B x M y T t (Fe 1-a Z a _{) b B x M y T t} X Z where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
W is one or more elements selected from Mn, T is one or more elements selected from the group consisting of Cu, Ag, Au, Pd, and Pt; Is Si,
One or more of Al, Ge, and Ga;
a, b, x, y, t, and z are 0 ≦ a ≦ 0.1, 75 atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%,
4 atomic% ≦ y ≦ 9 atomic%, t ≦ 5 atomic%, z ≦ 5 atomic%
It is.

In the Fe-based soft magnetic alloy having the above composition, 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 characteristics. In soft magnetic alloys of these compositions,
The value of b indicating the amount of Fe added or the value of b indicating the amounts of Fe and Co and / or Ni added is 93 atomic% or less. This is because if b exceeds 93 atomic%, it is 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 non-uniform and high magnetic permeability is obtained. This is because they cannot be obtained. Further, in order to obtain a saturation magnetic flux density of 10 kG or more, it is more preferable that b is 75 atom% or more. Therefore, the range of b is set to 75 to 93 atom%. Some of Fe is used for adjustment of magnetostriction, etc.
May be substituted with Co or Ni. In this case, the content is preferably 10% of Fe, more preferably 5% or less. Outside this range, the magnetic permeability deteriorates.

B has the effect of increasing the ability of the soft magnetic alloy to form an amorphous phase, the effect of preventing the crystal structure from becoming coarse, and the effect of suppressing the formation of a compound phase that adversely affects magnetic properties in the heat treatment step. It is believed that there is. Also, originally,
Zr and Hf hardly dissolve in α-Fe,
By quenching the entire alloy to make it amorphous, Zr and Hf
Is super-saturated, and 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, The magnetostriction of the ribbon can be reduced. Further, in order to precipitate a microcrystalline phase and to suppress the coarsening of the crystal grains of the microcrystalline phase, it is considered 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 of Zr, Hf, N
It is considered that the incorporation of an M element such as b suppresses the formation of an Fe-M-based compound that degrades the soft magnetic properties. Therefore, it is important to add B to the Fe-Zr (Hf) -based alloy. If x, which indicates the amount of B added, is less than 0.5 atomic%, the amorphous phase at the grain boundary becomes unstable, and a sufficient effect of addition cannot be obtained. X indicating the amount of B added is 1
When the content exceeds 8 atomic%, the tendency of boride formation in the BM system and the Fe-B system becomes strong, and as a result, heat treatment conditions for obtaining a fine crystal structure are restricted, and good soft magnetic characteristics are obtained. Can not be. By adding an appropriate amount of B in this manner, the average crystal grain size of the fine crystal phase precipitated is 30
nm or less.

To make it easier to obtain an amorphous phase,
It is preferable to include any of Zr, Hf, and Nb, which have particularly high amorphous forming ability, and a part of Zr, Hf, and Nb is partially replaced with other 4%.
It can be replaced with any of Ti, V, Ta, Mo, and W among the A to 6A group elements. Such an M element is a relatively slow diffusing species, and the addition of the M element is considered to have an effect of reducing the growth rate of fine crystal nuclei and an ability to form an amorphous phase, and is effective in making the structure finer.

However, if the value of y, which indicates the amount of the element M, is less than 4 atomic%, the effect of reducing the nucleus growth rate is lost, and as a result, the crystal grain size becomes coarse and good soft magnetism is obtained. Absent. In the case of the Fe-Hf-B alloy, the average crystal grain size at Hf = 5 atomic% is 13 nm, whereas Hf =
At 3 atomic%, it is coarsened to 39 nm. On the other hand, when y indicating the addition amount of the M element exceeds 9 atomic%, the MB type or F
The tendency of formation of e-M-based compounds increases, and good characteristics cannot be obtained. In addition, the ribbon-like alloy after liquid quenching becomes brittle, and it becomes difficult to process the alloy into a predetermined core shape. Therefore,
The range of y was 4 to 9 atomic%. Above all, Nb and Mo
Has a small absolute value of the free energy of oxide formation, is thermally stable, and is hardly oxidized during production. Therefore, when these elements are added, the production conditions are easy, the production can be performed at low cost, and the production cost is also advantageous. When the soft magnetic alloy is manufactured by adding these elements, specifically, at the tip of a nozzle of a crucible used for rapidly cooling a molten metal, an inert gas is partially supplied to the tip of a crucible. Or in an atmosphere of air.

It is preferable that one or more elements X of Si, Al, Ge, and Ga are contained in an amount of 5 atomic% or less. These are known as metalloid elements, and these metalloid elements are bcc mainly composed of Fe.
Solid solution in the phase (body-centered cubic phase). If the content of these elements exceeds 5 atomic%, it is not preferable because the magnetostriction increases, the saturation magnetic flux density decreases, or the magnetic permeability decreases. These elements have the effect of increasing the electrical resistance of the soft magnetic alloy and reducing iron loss, but Al has a particularly large effect. Ge and Ga have the effect of reducing the crystal grain size. Therefore, among Si, Al, Ge, and Ga, A
l, Ge, and Ga are particularly effective when added, and Al, G
e, Ga alone or Al and Ge, Al and Ga,
It is more preferable to make a composite addition of Ge and Ga, or Al, Ge and Ga.

Further, one of Cu, Ag, Au, Pd, and Pt
When containing at least 5 atomic% of one or more elements,
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,
Cu 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, it is considered that the obtained composition has a fine grain structure. From the above viewpoints, similar effects can be expected for elements other than these elements that lower the crystallization temperature.

Further, the present invention provides a composition represented by the following formula:
That is, it is more suitable for producing a soft magnetic alloy having a composition containing Zr and Nb as essential components. Fe _b Zr _d Nb _{e B x} where 80 atomic% ≦ b, 5 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d / (d + e) ≦ 2.5 / 6,5 atomic% ≦ x ≦ 12.5 atomic%.

In the Fe-based soft magnetic alloy having such a composition, b representing the composition ratio of Fe is 80 atomic% or more.
If b is less than 80 atomic%, it is not preferable because the saturation magnetic flux density cannot be increased to 1.5 T or more. Also, F
The composition ratio b of e is more preferably 83 atomic% or more, and further preferably 85 atomic% or more and 86 atomic% or less. In order to obtain a saturation magnetic flux density of 1.5 T or more, it is necessary to fill as much Fe as possible after satisfying the addition range of the other additional elements. In view of the amount of other additional elements, 80 atomic% is required. By containing more than the above amount, a saturation magnetic flux density of 1.5 T or more can be easily obtained as shown in Examples described later. When b is 85 atomic% or more, the saturation magnetic flux density can be 1.6 T or more. The reason why b is set to 86 atomic% or less is that if b exceeds 86 atomic%, it becomes difficult to obtain an amorphous single phase by a liquid quenching method, and as a result, the structure of the alloy obtained after heat treatment Is not preferable because a high magnetic permeability cannot be obtained due to non-uniformity. Further, a part of Fe may be replaced with Co or Ni for adjustment of magnetostriction or the like. In this case, the content is preferably 10% of Fe, more preferably 5% or less. Outside this range, the magnetic permeability deteriorates.

In the present invention, in order to easily obtain an amorphous phase, it is necessary to simultaneously include Zr and Nb having high amorphous forming ability. Further, it is considered that B has the effect of increasing the amorphous forming ability of the Fe-based soft magnetic alloy according to the present invention and the effect of suppressing the formation of a compound phase that adversely affects magnetic properties in the heat treatment. B addition is essential. Zr and Nb are important elements for obtaining an amorphous phase when quenched from the molten alloy. From this amorphous phase, bcc-Fe phase fine crystal grains are precipitated by heat treatment to 1.5T. It is important to achieve both the above high saturation magnetic flux density and high magnetic permeability.

Let the composition ratio of Zr be d and the composition ratio of Nb be e
When the total amount (d + e) is 5 atomic% or more, a necessary amount of the amorphous phase cannot be obtained unless these elements are added. The value of (d + e) is 7.5 atomic%.
Exceeding the range is not preferred because the saturation magnetic flux density deteriorates and the soft magnetic characteristics also deteriorate. Further, by setting the composition ratio of Zr and Nb in the range of 1.5 / 6 ≦ d / (d + e) ≦ 2.5 / 6, the magnetic permeability and saturation of the high saturation magnetic flux density and low iron loss Fe-based soft magnetic alloy can be improved. The magnetic flux density is further improved, and the iron loss is extremely small. In particular, the iron loss is remarkably reduced in a low frequency range of several hundred Hz or less, and the change with time of the iron loss is also small. Further, the total amount of Zr and Nb is more preferably 5 atomic% or more and 7.0 atomic% or less, and still more preferably 5.7 atomic% or more and 6.5 atomic% or less. More preferably, the composition ratio of Zr and Nb is d / (d + e) = 2/6. Further, the composition ratio d of Zr is preferably 0.5 atomic% or more and 3.5 atomic% or less, more preferably 1.5 atomic% or more and 2.5 atomic% or less. Nb composition ratio e
Is preferably not less than 3 atomic% and not more than 5.5 atomic%, more preferably not less than 3.5 atomic% and not more than 5.0 atomic%.

As described above, B also has the ability to form an amorphous phase, and thus contributes to the formation of an amorphous phase together with Zr and Nb. Since the tendency to form a compound phase that deteriorates magnetic properties is increased, the composition ratio z is set to 5 to 12.5 at%, more preferably to 6 to 9.5 at%, and still more preferably to 8 at%. % To 9 atomic%.

Although Zr and Nb hardly form a solid solution with bcc-Fe, the alloy is rapidly cooled to become amorphous, and then heat-treated to be crystallized, thereby converting Zr and Nb into crystals. Super-saturated solid solution in bcc-Fe.
By adjusting the solid solution amount of these elements by this heat treatment and precipitating as a fine crystalline structure, the magnetostriction of the obtained high saturation magnetic flux density and low iron loss Fe-based soft magnetic alloy is reduced, and the soft magnetic properties are improved. There is action. Further, in order to precipitate a fine crystalline structure and to suppress the coarsening of the crystal grains in the fine crystalline structure, it is necessary to leave an amorphous phase which may hinder the crystal grain growth at the grain boundaries. it is conceivable that. Further, the grain boundary amorphous phase becomes b
Fe-Zr or Fe-N which degrades soft magnetic characteristics by taking in Zr and Nb discharged from the cc-Fe phase
It is considered that the formation of the b-based compound is suppressed. Therefore,
Fe-Zr-based or Fe-Nb-based or Fe-Zr-
It is important to add B to an Nb-based alloy. The Fe-based soft magnetic alloy having any one of the above-mentioned compositions according to the present invention contains C
It is also possible to add a platinum group element such as r, Ru, Rh, and Ir. If these elements are added in an amount of more than 5 atomic%, the saturation magnetic flux density is significantly deteriorated.

The present invention is particularly suitable for the production of a soft magnetic alloy having a composition represented by the following formulas, that is, Zn is essential, or Zn is essential and Zr and Nb are essential. It is. _{(Fe 1-a Z a)} b Zr d Nb e B x Zn f Fe b Zr d Nb e B x Zn f (Fe 1-a Z a) b Zr d Nb e B x Zn f M 'u Fe b Zr _{d Nb e B x Zn f M} 'u (Fe 1-a Z a) b B x M y Zn f Fe b B x M y Zn f where, Z is Co, a or Ni,
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, and a ≦ 0.05, 80 atomic% ≦
b, 1.5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦ e
≦ 5.0 at%, 5 at% ≦ x ≦ 12.5 at%, 5 at% ≦ y ≦ 7.5 at%, 0.025 at% ≦ f ≦ 0.2 at%, u ≦ 5 at% 5.0 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d / (d + e) ≦ 2.5 / 6.

[0049] Here, the soft magnetic alloy having a composition represented by the formula is, in particular different from the Fe _b Zr _d Nb _e soft magnetic alloy of B _x a composition as described above, in that Zn is added is there.
Furthermore, in addition to Fe, Co and / or Ni may be contained as an element bearing magnetism.
One or more elements M ′ selected from u, Rh, and Ir may be contained, and Ti, Zr, Hf,
V, Nb, Ta, Mo, W, and Mn, in which at least one element selected from the group consisting of one or two or more elements M is added.

The Zn content in the soft magnetic alloy having a composition essentially containing Zn is 0.025 atomic% or more.
And the range of 0.2 atomic% or less is preferable. If added in this range, the coercive force and iron loss can be reduced and the magnetic permeability can be increased without lowering the high saturation magnetic flux density of 1.5 T or more. In addition, the content of Zn is 0.034 atomic% or more and 0.160 atomic%.
The range of at most atomic% is more preferable, and if it is within this range, a soft magnetic alloy having lower iron loss, higher saturation magnetic flux density and less change with time can be obtained.

However, since Zn has a melting point of 419.5 ° C. and a boiling point of 908 ° C., when the Fe-based soft magnetic alloy having the above composition is melted in a crucible, the melting temperature is 124 ° C.
Since the temperature is set at about 0 to 1350 ° C., most of the Zn evaporates and disappears. In order to rapidly cool the molten alloy having the above-described composition into an amorphous alloy, the molten metal is sprayed onto a cooling body such as a cooling roll to be rapidly cooled, or an atomizing method of jetting into a cooling gas is performed. In order to allow the quenched alloy to contain the above amount in the above range, it is necessary to add Zn in an amount exceeding the Zn amount as an alloy composition to be put into the crucible. That is, according to the study of the present inventors, 1
It has been found that when using a molten metal at a temperature of about 240 to 1350 ° C. to obtain an alloy in the form of a ribbon or a powder from the molten metal by a quenching method, it is preferable to set the input amount to about 20 times or more the target composition.

FIG. 3 shows an example of a manufacturing apparatus for obtaining the above-mentioned soft magnetic alloy containing Zn as an essential component in the form of a thin strip. The chamber is connected to a vacuum pump 1 via an exhaust pipe 1a and can be evacuated. Inside 2, a cooling roll 3 made of copper or steel is installed rotatably. A crucible 6 having a nozzle 5 made of quartz or the like is provided above the cooling roll 3. A gas supply source 7 is connected to the crucible 6 via a gas supply pipe 7 a so that an Ar gas pressure can be applied to the crucible 6. A gas supply source 8 for adjusting the inside of the chamber 2 to a reduced pressure atmosphere of a non-oxidizing gas such as Ar gas is separately connected to the chamber 2 via a gas supply pipe 8a. A lid member is attached to the upper end of the crucible 6, and the inside of the crucible 6 to which the tip of the gas supply pipe 7 a is connected so as to penetrate the lid member is pressurized separately from the internal pressure of the chamber 2. It is configured to be able to.

A heater 9 is provided on the outer periphery of the bottom of the crucible 6 to heat and melt the alloy raw material put into the crucible 6 to obtain a molten metal. By applying an Ar gas pressure to the inside of the crucible 6 through the nozzle 5, the molten metal is blown out through the nozzle 5 onto the surface of the rotating cooling roll 3, and a thin strip is provided on the side of the cooling roll 3 as shown by reference numeral 11 in FIG. Is configured to be obtained.

In order to improve corrosion resistance, Cr, R
It is also possible to add one or more elements M ′ selected from u, Rh, and Ir. If these elements are added in an amount of more than 5 atomic%, the saturation magnetic flux density is significantly deteriorated.

It should be noted that the Fe of each of the composition systems according to the present invention is
In addition to the base soft magnetic alloy, Y, La, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
y, Ho, Er, Tm, Yb, Lu, Zn, Cd, I
n, Sn, Pb, As, Sb, Bi, Se, Te, L
The magnetostriction of the soft magnetic alloy obtained by adding elements such as i, Be, Mg, Ca, Sr, and Ba can also be adjusted. In addition, in the soft magnetic alloys of the respective composition systems, H,
Of course, unavoidable impurities such as N, O, and S can be regarded as having the same composition as the soft magnetic alloy obtained in the present invention even if they contain them to such an extent that desired characteristics are not deteriorated.

[0056]

(Example 1) First, a ribbon of an alloy mainly composed of an amorphous phase was prepared by a single roll liquid quenching method. That is, the molten metal is jetted from a nozzle placed on one rotating steel roll onto the roll by the pressure of argon gas, and rapidly cooled to obtain a ribbon. The width of the ribbon prepared as described above was about 15 mm, and the thickness was about 20 μm.
Next, the obtained ribbon is heated in a vacuum at a rate of 180 ° C. /
Minutes, a heat treatment temperature of 535 ° C., and a holding time of 5 minutes.
Was performed to precipitate a fine crystalline structure to produce ribbons of Fe-based soft magnetic alloys having various compositions. With respect to the obtained thin ribbon of the soft magnetic alloy, the magnetic permeability (μ ′) at 1 kHz and the saturation magnetic flux density (B
₁₀ ) The residual magnetization (Br) was measured. The magnetostriction constant (λ _s ) was measured for a part of the obtained ribbon. Here, the measurement of the magnetic permeability is performed by processing the obtained ribbon, and setting the outer diameter to 10 mm.
It was formed into a ring shape having an inner diameter of 6 mm and an inner diameter of 6 mm. The measurement conditions of the magnetic permeability (μ ′) were 5 mOe and 1 kHz. The coercive force (Hc) and the saturation magnetic flux density (B ₁₀ )
The measurement was performed using an H loop tracer.

Further, the heat treatment temperature (holding temperature) at which the coercive force (Hc) was minimum and the magnetic permeability (μ ') was maximum when the first heat treatment was performed in the range of 500 ° C. to 700 ° C. was measured. Further, with respect to a part of the obtained ribbon, an average crystal grain size of crystal grains in a fine crystal structure was obtained by a transmission electron microscope. Further, a part of the quenched ribbon before the heat treatment was subjected to differential thermal analysis (DTA measurement) to determine the crystallization temperatures (T _x1 , T _x2 , T _x2 , T _x2 , T _{x1 ′} ) was measured to determine the crystallization temperature interval (ΔT _x ). These results are shown in FIGS. 17 to 28 show various characteristics of the soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic%. In FIGS. 17 to 28, the mark ○ indicates bc in the ribbon in the quenched state.
The ribbon indicates the diffraction peak of the (200) plane of the c-Fe phase, and the closed circle indicates the bcc-
The ribbon shows no diffraction peak of the (200) plane of the Fe phase. In other words, the ribbons marked with ○ are heat-treated quenched ribbons in which a crystalline phase is precipitated in a part of the amorphous phase. Was heat treated.

As shown in FIG. 17, the soft magnetic alloy in which Zr + Nb = 6 atomic% has a coercive force (Hc) of 38 to 8400 mOe. Here, the coercive force (Hc) of 70 mOe or less indicates that Zr is 0.5 at% or more, preferably 1 at% or more, B is 10 at% or less, and F
The alloy has a composition range in which the sum of e and Nb is 90 atomic% or less. In addition, a coercive force (Hc) of 50 mOe or less is obtained when Zr is 1.5 atomic% or more and 3.5 atomic% or less and B
Is 6.5 atomic% or more and 9.5 atomic% or less, preferably 6.
5 atomic% or more and 9 atomic% or less, and the total of Fe and Nb is 8
The alloy has a composition range of 9 at% to 90 at% (Fe is 84.5 at% to 87.5 at%). Further, the coercive force (Hc) of 40 mOe or less is due to Zr
Is 1.5 atomic% or more and 2.5 atomic% or less, preferably 2.
0 atomic%, B is 8 atomic% or more and 9 atomic% or less, and F
the sum of e and Nb is 89 atomic% or more and 89.5 atomic% or less;
Preferably, 89.5 atomic% (Fe is 85 atomic% or more and 86 atomic% or more.
(Atomic% or less).

Next, as shown in FIG. 18, Zr + Nb =
The soft magnetic alloy of 6 atomic% has a magnetic permeability (μ ′) of 900 to 59000. Here, an alloy having a magnetic permeability (μ ′) of 30,000 or more is an alloy having a composition range in which Zr is 1 at% or more, B is 10 at% or less, and the total of Fe and Nb is 90 at% or less. . In addition, a magnetic permeability (μ ′) of 40000 or more indicates that Zr is 1 to 3 atomic%, B is 7.5 to 9.5 atomic%, and the total of Fe and Nb is 89 atom% or more and 90 atom%
Or less (Fe is 84.5 atomic% or more and 86.5 atomic% or less)
Is an alloy having a composition range of Further, a magnetic permeability (μ ′) of 50,000 or more is expressed when Zr is 1.5 atomic% or more and 2.5 atomic% or more.
Atomic% or less, B is 8 atomic% or more and 9 atomic% or less, and the total of Fe and Nb is 89 atomic% or more and 90 atomic% or less (F
e is an alloy having a composition range of 85 atomic% to 86 atomic%.

Therefore, as is apparent from FIGS. 17 and 18, Zr + Nb = 6 atomic% is satisfied, and Zr is 1.
In the range of 5 atomic% to 2.5 atomic%, that is, Zr /
The range of (Zr + Nb) is not less than 1.5 / 6 and not more than 2.5 / 6, B is not less than 8 atomic% and not more than 9 atomic%,
Fe is 80 atom% or more, and the total of Fe and Nb is 89
Atomic% or more and 90 atomic% or less (Fe is 85 atomic% or more and 86 atomic% or less.
(Atomic% or less) of the soft magnetic alloy
It has excellent soft magnetic properties due to its high magnetic permeability (μ ′) of 50,000 or more and low coercive force (Hc) of 40 mOe or less.

Next, as shown in FIG. 19, Zr + Nb =
6 is an atomic% soft magnetic alloy shows a saturation magnetic flux density of 1.53~1.67T (B _10). Saturation magnetic flux density (B ₁₀ )
Depends on the composition ratio of Fe, and the correlation with the composition ratio of Zr, Nb, and B is not clear. However, when the concentration of Fe is high, the saturation magnetic flux density (B ₁₀ ) tends to increase. In the above composition range, it is possible to have both a saturation magnetic flux density (B ₁₀ ) of 1.5 to 1.6 T or more and a high magnetic permeability (μ ′) of 40000 to 50,000 or more. As shown in FIG. 20, the soft magnetic alloy in which Zr + Nb = 6 atomic% has a remanent magnetization (B
r). For the residual magnetization (Br), F
The correlation with the composition ratio of e, Zr, Nb, and B is not clear. Further, as shown in FIG. 21, Zr + Nb = 6 at%
It can be seen that in the soft magnetic alloy, the average crystal grain size of the bcc-Fe phase is in the range of 10 to 12 nm.

Among them, the reason why the average crystal grain size is 11 nm or less is that Zr is 4 at% or less and B is 5.5 to 10 at%, preferably 6 to 9 at%, And the total of Fe and Nb is 88 to 92 atomic%, preferably 89 to 92 atomic% (Fe is 84 to 88.5 atomic%, preferably 85 to 88 atomic%. ) Are soft magnetic alloy ribbons, and it is understood that these ribbons have a particularly fine crystalline structure. This composition range includes the optimum composition range of the coercive force (Hc) and the magnetic permeability (μ ′) shown in FIGS. 17 and 18, and the finer the average crystal grain size of the bcc-Fe phase is, It is suggested to show excellent soft magnetic properties.

As shown in FIG. 22, Zr + Nb =
In the case of the soft magnetic alloy of 6 atomic%, the magnetostriction constant (λ _s ) is in the range of −14 × 10 ^{−7 to} 17 × 10 ⁻⁷ , which is a good value. In addition, the isolines with zero magnetostriction are included in the region having the highest magnetic permeability (μ ′) shown in FIG. The magnetostriction constant (λ _s ) tends to depend on the composition ratio of B. When B is 8 atomic% or more and 9 atomic% or less, the magnetostriction constant (λ _s ) is almost zero. FIG. 23 shows that Zr + N
The graph shows the optimum first heat treatment temperature (holding temperature) for obtaining the minimum coercive force (Hc) in a soft magnetic alloy where b = 6 at%. Among them, the heat treatment temperature is 525 ° C
Below, the coercive force (Hc) becomes smaller because Zr is 1 atomic% or more and 3 atomic% or less and B is 7.5 atomic% or more and 9.5 atomic%.
Atomic% or less, and the total of Fe and Nb is 89 atomic% or more and 9
It is found that the ribbon is 0 atomic% or less (Fe is 84.5 atomic% or more and 86.5 atomic% or less), and the heat treatment temperature is also kept low.

FIG. 24 shows that Zr + Nb = 6 atomic%.
1 shows the optimum first heat treatment temperature (holding temperature) for obtaining the maximum magnetic permeability (μ ′) in the soft magnetic alloy. Among them, the magnetic permeability (μ ′) increases when the heat treatment temperature is 525 ° C. or less because Zr is 1.5 to 2.5 atomic%, B is 8 to 9 atomic%, and The total of Fe and Nb is 89 atomic% or more and 90 atomic%.
It can be seen that this is a thin ribbon of less than or equal to 85 at% (86 at% or less). Also, from FIGS. 23 and 24, Zr
Is 0.5 atomic% to 3.5 atomic%, B is 7 atomic% to 10.5 atomic%, and the total of Fe and Nb is 9 atomic%.
When the holding temperature of the first heat treatment is 550 ° C. or less, the ribbon of the soft magnetic alloy of 0 atomic% or less has an optimum coercive force (Hc).
And the magnetic permeability (μ ′), and the composition range was determined by the coercive force (H) shown in FIGS. 17, 18 and 21.
c), almost the optimal composition range of the magnetic permeability (μ ′) and the average crystal grain size of the bcc-Fe phase, and if the first heat treatment temperature is 550 ° C. or less, the bcc-Fe phase It is suggested that the average crystal grain size is kept fine and that it exhibits excellent soft magnetic properties.

Next, FIG. 25 shows the crystallization temperature (T _x1 ) of the bcc-Fe phase, FIG. 26 shows the crystallization temperature (T _x2 ) of another compound phase, and FIG. 27 shows the crystallization temperature of another compound phase. Shows the crystallization temperature (T _{x1 ′} ). The relationship between these crystallization temperatures is T _x1 <
T _{x1 ′} <T _x2 . FIG. 28 shows the crystallization temperature interval (ΔT _x : ΔT _x = T _x2 −T _x1 ). As shown in FIG. 25, T _x1 is in the range of 464 to 500 ° C.
It depends on the composition ratio of Nb and Zr and not on the composition ratio of B. 17 and FIG. 18, the range in which the coercive force (Hc) and the magnetic permeability (μ ′) show good values [Zr / (Zr + Nb) is 1.5 / 6 or more and 2.5 / 6 or less, and B is 8 Atomic% or more and 9 atomic% or less, Fe is 80 atomic%
As described above, T _x1 is in the range of 480 to 490 ° C.]

As shown in FIG. 28, the crystallization temperature interval (ΔT _x ) indicates a range of 313 to 344 ° C., and as the B composition ratio decreases, the crystallization temperature interval (ΔT _x ) decreases. ΔT _x ) tends to be wide. In particular, when Zr is 1 atomic% or more and 2.5 atomic% or less and B is in the range of 9.5 atomic%, the crystallization temperature interval of 330 ° C. or more (Δ
Since _Tx ) is shown, only the bcc-Fe phase is precipitated during the heat treatment, and the precipitation of the compound phase can be suppressed, and deterioration of the soft magnetic properties of the soft magnetic alloy can be prevented. In FIG. 27, a plot without a subscript indicates an alloy in which the crystallization temperature (T _{x1 ′} ) of another compound phase was not observed.
It can be seen that the alloy in which T _{x1 ′} does not exist generally has better magnetic properties.

As described above with reference to FIGS. 17 to 28,
When the total amount of Zr and Nb is 6 atomic%, Zr is set to 1.
5 to 2.5 atomic%, B is 8 to 9 atomic%, and the total amount of Fe and Nb is 89 to 90 atomic% (Fe is 85 to 86 atomic%.) )) And exhibit excellent soft magnetic properties.
It was clarified that excellent soft magnetic properties were exhibited when was set to 2 atomic%. As shown in FIGS. 17 to 28, in the above composition range, no precipitation of the (200) plane of Fe was observed in the quenched state, and a thin ribbon (indicated by a solid circle) substantially becoming an amorphous single phase was observed. ) Are present, and it can be seen that the thin strip (marked with ○) in which the amorphous phase and the crystalline phase are mixed is mainly scattered outside the above range. Thus, it has been clarified that when the first heat treatment is performed on the ribbon mainly composed of the amorphous phase in the quenched state, the ribbon tends to exhibit excellent soft magnetic properties. Specifically, Fe _85.5 Zr ₂ Nb ₄ B _8.5 , Fe _{85.5
85 Zr 1.75 Nb 4.25 B 9,} Fe 85 .25 Zr 1.75 Nb 4.25 B
_8.75 , Fe _85.75 Zr _2.25 Nb _3.75 B _8.25
It can be seen that the e-based soft magnetic alloy exhibits particularly excellent soft magnetic properties.

(Example 2) A soft magnetic alloy ribbon sample was prepared by a single roll liquid quenching method using the apparatus shown in FIG.
That is, a molten metal of a predetermined component is ejected from a nozzle placed on one rotating copper cooling roll onto the cooling roll through a quartz nozzle by the pressure of argon gas, and rapidly cooled to form a ribbon. I got Here, the target composition of 20
A soft magnetic alloy sample containing Zn in the range of 0.025 to 0.2 atomic% was prepared by introducing about twice as much raw material Zn into a crucible to produce a ribbon. The width of the ribbon prepared as described above was about 15 mm, and the thickness was about 20 μm. Further, the quenched ribbon is made of an alloy mainly composed of amorphous. However, in order to precipitate fine crystal grains of bccFe and improve soft magnetic properties, the ribbon is heated to a crystallization temperature or higher and then cooled. In the heat treatment of each example, a Fe-based soft magnetic alloy ribbon sample and each comparative sample were obtained.

The magnetic permeability of the soft magnetic alloy ribbon sample obtained as described above was determined by processing the ribbon and measuring the outer diameter of 10 mm and the inner diameter of 6 mm.
, And wound on a stack of these, and measured using an impedance analyzer. The measurement conditions of the magnetic permeability (μ ′) were 5 mOe and 1 KHz. Coercive force (Hc) and magnetic flux density (B ₁₀₎ were measured at 10 Oe by DC B-H loop tracer. Incidentally, B ₁₀ is almost equivalent numbers and saturation magnetic flux density (Bs).

FIG. 4 shows a composition system similar to the composition system of the present invention.
Fe_bZr_dNb_eB_xThe coercive force of samples with different compositions was measured
The results and 0.034 to 0.3 for the alloy sample of this composition system.
(Fe of a composition system in which Zn is added in a range of 142 atomic%.
_{c / 100}Zr_{d / 100}Nb_{e / 100}B_{f / 1 00})_100-zZn_zComposition
The triangular composition diagram showing the results of measuring the coercive force of each sample
is there. In addition, in the sample to which Zn was added,
The sample shown in ()_0.855Zr_0.02Nb_0.04B_0.085)
_99.944Zn_0.056A sample having a composition of
_0.855Zr_0.02Nb_0.04B_0.085)_98.892Zn_0.108Pair of
The sample shown in FIG._0.855Zr_0.02Nb
_0.04B_0.085)_99.859Zn_0.141Sample of composition, shown in
The sample is (Fe_0.8575Zr_0.02Nb_0.04B_0.0825)_99.96
Zn_0.04A sample having a composition of_0.8575Z
r_0.02Nb_0.04B_0.0825)_99.875Zn_{0.12 Five}Composition test
The sample shown in the_0.8575Zr_0.02Nb_0.04B
_0.0825)_{99.87 Five}Zn_{0.13 Three}Sample of composition, sample shown in
Is (Fe_0.86Zr_0.02Nb_0.04B_0.08)_99.866Zn
_0.034A sample having a composition of_0.86Zr
_0.02Nb_0.04B_{0 .08})_{99.88 Three}Zn_0.117A sample of the composition of
The sample shown in ()_0.86Zr_0.02Nb_{0. 04}B_0.08)
_99.858Zn_0.142Is a sample having a composition of

In FIG. 4, Zr and Nb are 6 atomic% in total.
In the FeZrNbB-based alloy sample contained, even when B is in the range of 5 to 12.5 at%, it is apparent that by setting the range of 6 to 9.5 at%, a low coercive force of less than 50 mOe is exhibited. And B is within the range of 8 to 9.5 in this range.
Atomic%, Zr is 1.5-2.5 atomic%, Fe + Nb is 89
Particularly low coercivity below 40 mOe in the range of ９０90 at%. In addition, for samples of these compositions,
Samples to which n was added exhibited a low coercive force of less than 100 mOe. In addition, the coercive force is particularly 40 mO.
It has been found that when Zn is added to samples around e and around 50 mOe, the value of the coercive force tends to decrease. In addition, in the sample indicated by the symbol “〇” in FIG.
This is a sample in which diffraction from the (200) peak of bccFe was caused due to precipitation of a part of Fe crystal grains. Further, the sample indicated by ● was a sample in which a diffraction peak from a crystal phase did not appear when X-ray observation was performed in a state where a ribbon was obtained by rapid cooling, which means that the sample was completely amorphous.
Looking at the magnetic properties of each of these samples, the coercive force of the sample that was completely amorphous after quenching was lower.

FIG. 5 is a triangular composition diagram showing the result of measuring the magnetic permeability (μ ′: real part of the complex magnetic permeability) at 1 kHz for the sample described above. In the samples having the composition of the present invention and containing Zn in the range of 0.034 to 0.142 atomic%, all of them show excellent magnetic permeability exceeding 30,000, and Zn in the range of 0.04 to 0.142 atomic%. In the samples added in the range, the magnetic permeability exceeded 40,000.

FIG. 6 is a triangular composition diagram showing a saturation magnetic flux density (B ₁₀ ) obtained from a magnetization curve obtained by applying an applied magnetic field of 10 Oe, and FIG. 7 is a residual magnetic flux density (Br) of the previous sample.
3 is a triangular composition diagram showing the measurement results of FIG. It is clear that if the Zr and Nb contents are similar to the composition system of the present invention, a high saturation magnetic flux density exceeding 1.5 T can be obtained. All of the samples to which Zn was added to the alloy samples in the range of 0.034 to 0.142 atomic% showed excellent saturation magnetic flux densities exceeding 1.6 T. Therefore, even if Zn is added within the range of the present invention, the saturation magnetic flux density hardly changes, and it is clear that the value is maintained at a high value. From FIG. 7, Zn was added in the range of 0.034 to 0.142 atomic%.
It can be seen that each of the samples has a high residual magnetic flux density of 0.8 T or more.

FIG. 8 shows the first crystallization temperature (T _x1
Is a triangular composition diagram showing the crystallization temperature of bccFe), FIG. 9 is a triangular composition diagram showing the intermediate crystallization temperature of the previous sample (T _x1 ′ is the crystallization temperature of the compound phase), and FIG. FIG. 11 is a triangular composition diagram showing a second crystallization temperature (T _x2 is the crystallization temperature of the compound phase), and FIG. 11 is a triangular composition diagram showing ΔT _x represented by T _x2 −T _x1 .

Hereinafter, the first crystallization temperature, the intermediate crystallization temperature, and the second crystallization temperature will be described. When an alloy of the composition system according to the present invention, which is mainly composed of an amorphous phase produced by rapid cooling, is heated, first, bc
An exothermic reaction accompanying the crystallization of the cFe phase occurs, and the crystallization of other compound phases (Fe ₃ B or Fe ₂ B
Exothermic reaction occurs between them, and further exothermic reaction occurs between them depending on the composition. The first exothermic peak is b
This is the largest exothermic peak due to the crystallization of ccFe,
The second exothermic peak corresponds to a first crystallization temperature, the second exothermic peak is a small exothermic peak for forming a compound phase, corresponds to an intermediate crystallization temperature, and the third exothermic peak is a small exothermic peak for forming another compound phase. A peak corresponding to the second crystallization temperature. However, the second exothermic peak may not appear depending on the composition, and the samples indicated by-in FIG. 9 are samples in which the second exothermic peak does not appear (the intermediate crystallization temperature T _x1 ′ does not appear). Sample). Note that a composition in which the second exothermic peak does not appear has better magnetic characteristics. It can be seen that even if Zn is added to these composition systems, the crystallization temperature hardly changes.

The crystallization temperature interval Δ thus obtained
It is preferable that the T _x and 200 ° C. or higher. Each of ΔT _x shown in FIG. 11 is 200 ° C. or higher, and when considered in conjunction with the magnetic permeability data of FIG. 5, ΔT _x is 320 to 340.
It is understood that ΔC is most preferable. ΔT _x is 20
If the temperature is 0 ° C. or higher, the interval between the crystallization temperatures of the bccFe phase and the compound phase is widened, so that it is easy to heat-treat the alloy under optimum conditions, and only the bccFe phase is precipitated to separate other compounds. Precipitation is suppressed, and soft magnetic properties are easily improved. Therefore, the heat treatment temperature of the alloy is between the first crystallization temperature and the second crystallization temperature (the temperature between T _x1 and T _x2 ).
It is preferable to carry out.

FIG. 12 shows a composition system similar to the composition of the present invention.
FIG. 4 is a triangular composition diagram showing the crystal grain size of a sample of a composition system not containing n. From the test results described below, it was found that the addition of Zn in the composition range of the present invention to this composition system slightly reduced the crystal grain size. The inventors have confirmed. Therefore, it can be seen that even in the alloy of the composition system of the present invention, crystal grains having a particle diameter of 12 nm or less, preferably 11 nm or less can be obtained.
FIG. 13 is a triangular composition diagram showing the magnetostriction (λs) of a sample of a composition system similar to the composition of the present invention but not containing Zn, and the magnetostriction is the same even when Zn is added to this composition system. Have been confirmed by the present inventors. Accordingly, it can be seen that even in the alloy of the present invention in which Zn is added to the alloy of the composition shown in FIG.

FIG. 14 shows the dependence of the crystal grain size (D) on the Zn concentration of the alloy sample of the present invention to which Zn is added. There was a tendency for the crystal grain size to slightly decrease due to the effect of Zn addition. FIG. 15 shows the Zn concentration dependency of the magnetostriction (λs) of the alloy sample of the present invention to which Zn is added. There is a clear tendency for magnetostriction to decrease due to the Zn addition effect, but the amount of change is slight.

FIG. 16 shows that an alloy sample having a composition of Fe _85.75 Zr ₂ Nb ₄ B _8.25 contains Zn at 0.12 atomic% or 0.13 atomic%.
The results obtained by measuring the iron loss of the sample to which atomic% was added using an AC magnetization characteristic measuring apparatus are shown in comparison with the values of the ribbon sample having the composition of Fe ₇₈ Si ₉ B ₁₃ of the comparative example. As is clear from the results shown in FIG. 15, it was clarified that the iron loss of the sample obtained by performing the manufacturing method of the present invention showed a smaller iron loss than the sample of the comparative example. The iron loss of the sample obtained by the practice of the present invention was 0.1 W / kg at 1.4T.
Is clearly lower than that of the silicon steel sheet.
It is clear that this is an excellent value of about 10, which is a fraction of that of the Fe-based amorphous.

(Embodiment 3) In the same manner as in Embodiment 1, Fe
_85.5 Zr ₂ Nb ₄ B _8.5 , Fe ₇₈ Si ₉ B ₁₃ (commercial product: amorphous alloy) After preparing a quenched ribbon having the composition,
Heat treatment. On the other hand, (Fe
_0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.88 Zn _0.12 ,
(Fe _0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.87 Zn
After preparing a quenched ribbon having a composition of _0.13 , a first heat treatment was performed, and the temperature was lowered to room temperature. The first heat treatment conditions for the ribbon here are Fe _85.5 Zr ₂ Nb ₄ B _8.5 , (F
e _{0.857 5} Zr _0.02 Nb _0.04 B _0.0825 ) _99.88 Zn _0.12 ,
(Fe _0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.87 Zn
_{For 0.13} , the heating rate was 180 ° C./min, and the holding time was 5
And 510 ° C, 525 ° C, and 51 ° C, respectively.
The test was performed under the condition of 0 ° C. As for Fe ₇₈ Si ₉ B ₁₃ , the temperature was increased at a rate of 180 ° C./min, a holding time of 120 minutes, and a holding temperature of 350 ° C.

Next, each of the obtained ribbons is subjected to a second heat treatment in the air. At this time, when the holding time at the holding temperature of 320 ° C. is changed in the range of 0 to 100 hours, coercive force and permeability and B ₁₀ and the Br (residual magnetization) were measured. Further, the dependence of the magnetic properties on the second heat treatment time was examined. The dependence of the magnetic properties on the second heat treatment time is as follows: the second heat treatment time (holding time), the coercive force, the magnetic permeability, and B ₁₀
And the rate of change of Br (residual magnetic flux density). B here
₁₀ is almost the same as the saturation magnetic flux density. Here, the second heat treatment condition for the ribbon was a temperature rising rate of 20 ° C./min when the temperature was raised from room temperature to a holding temperature of 320 ° C. The results are shown in Tables 1 to 4. FIG. 29 shows the coercive force (iHc).
Shows the time dependence of the second heat treatment. FIG. 30 shows the dependency of the magnetic permeability on the second heat treatment time. Table 1 to Table 4 and FIG.
30 to FIG. 30, the rate of change of each magnetic property indicates a rate of change with respect to the magnetic property when the second heat treatment time is 0 hour, that is, when the second heat treatment is not performed.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

[0085]

[Table 4]

As is clear from the results shown in Table 1 and FIG. 29, after the quenched ribbon having the composition of Fe ₇₈ Si ₉ B ₁₃ (commercial product: amorphous alloy) was subjected to the first heat treatment, Most of those subjected to the above second heat treatment are:
The coercive force exceeds 0.05 Oe, and the coercive force changes significantly as the second heat treatment time increases. In contrast, Fe _85.5 within the composition range of the present invention.
A quenched ribbon having a composition of Zr ₂ Nb ₄ B _8.5 (Fe
_0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.88 Zn _0.12 quenched ribbon, (Fe _0.8575 Zr _0.02 Nb _0.04
B _0.0825 ) _99.87 Zn _0.13 Each of the quenched ribbons having the composition of _0.13 was subjected to the first heat treatment, and then subjected to the second heat treatment for 1 hour or more. It can be seen that it has become smaller. This allows
In the range of compositions of the present invention, and samples out the production method of the present invention whereas the coercive force decreases, Fe ₇₈
In the comparative sample having the composition of Si ₉ B ₁₃ , the coercive force is significantly deteriorated. Therefore, from this result,
It is understood that the production method of the present invention can be applied to an alloy having a fine crystal structure, preferably, an alloy within the range of the composition of the present invention.

As is clear from the results shown in Table 2 and FIG. 30, the quenched ribbon having a composition of Fe ₇₈ Si ₉ B ₁₃ (commercial product: amorphous alloy) was subjected to the first heat treatment. The one subjected to the second heat treatment has a magnetic permeability of 5200 or less, and the magnetic permeability changes significantly as the second heat treatment time becomes longer. It is within the scope of the compositions of the present invention with respect to Fe _85.5 Zr ₂ Nb ₄ ribbons rapid cooling of B _8.5 a _{composition, (Fe 0 .8575 Zr 0.02 Nb} 0.04 B
_0.0825 ) _99.88 Zn _0.12 quenched ribbon
(Fe _0.8575 Zr _0.02 Nb _0.04 B _0.0825 ) _99.87 Zn
After applying the first heat treatment to each of the quenched ribbons having a composition of _0.13, the ribbons subjected to the second heat treatment are as follows:
It can be seen that the magnetic permeability is as large as 38500 or more, and that the rate of change of the magnetic permeability is small even when the second heat treatment time is long. Accordingly, in consideration of the results of Table 1 and FIG. 29, the sample which is within the range of the composition of the present invention and in which the production method of the present invention is performed has a small coercive force and an improved magnetic permeability. Alternatively, since the high value is maintained, the soft magnetic characteristics are improved. In contrast, Fe ₇₈ Si ₉
Comparative Example Samples of B ₁₃ having the composition, since the magnetic permeability when applying the manufacturing method of the present invention is greatly deteriorated, the production method is an alloy having a fine crystalline structure of the present invention, preferably in the range of the composition of the present invention Preferably applied to alloys within.

As is clear from the results shown in Table 3, Fe ₇₈
Si ₉ B _13: After that the thin strip of the rapidly solidified state of (commercially available amorphous alloy) having a composition subjected to the first heat treatment, which was subjected to a second heat treatment above, B ₁₀ 1.57 hereinafter a small addition, the rate of change of B ₁₀ is found to be small. It is within the scope of the composition of the present invention contrary _{Fe 85.5 Zr 2 Nb 4 B 8.} 5
_Quenched ribbon having the following composition: (Fe _0.8575 Zr _0.02 Nb
_0.04 B _{0.0825) 99.88} Zn _{0 .12} consisting ribbons rapid cooling of the _{composition, (Fe 0.8575 Zr 0.02 Nb 0.04} B 0.0825) 99 .87 Z
After thin strip rapidly solidified state of n _0.13 a composition were respectively subjected to the first heat treatment, those subjected to second heat treatment, B ₁₀
Is 1.57 or more, and the rate of change is small even when the second heat treatment time is long. This allows
In the range of compositions of the present invention, and sample the manufacturing method and practice of the invention, it maintains a much larger saturation magnetic flux density than Comparative Sample of Fe ₇₈ Si ₉ B _{1 3} having a composition I understand.

As is clear from the results shown in Table 4, Fe ₇₈
After subjecting the quenched ribbon of the composition of Si ₉ B ₁₃ (commercial product: amorphous alloy) to the first heat treatment and then to the second heat treatment, the second heat treatment time As the length increases, the residual magnetic flux density changes significantly. It is within the scope of the composition of the present invention contrary _{Fe 85.5 Zr 2 Nb 4 B 8.} 5
_Quenched ribbon having the following composition: (Fe _0.8575 Zr _0.02 Nb
_0.04 B _{0.0825) 99.88} Zn _{0 .12} consisting ribbons rapid cooling of the _{composition, (Fe 0.8575 Zr 0.02 Nb 0.04} B 0.0825) 99 .87 Z
The quenched ribbon having a composition of n _0.13 was subjected to the first heat treatment, and then subjected to the second heat treatment.
It can be seen that the rate of change of the residual magnetic flux density is small even if the heat treatment time is long. Thereby, the sample which is within the range of the composition of the present invention and in which the production method of the present invention is performed can improve the soft magnetic properties and increase the residual magnetic flux density. On the other hand, in the comparative sample having the composition of Fe ₇₈ Si ₉ B _13, it can be seen that when the manufacturing method of the present invention is applied, the residual magnetic flux density can be increased, but the soft magnetic characteristics are significantly deteriorated. From the results of FIGS. 29 to 30 and Tables 1 to 4, if the manufacturing method of the present invention is applied to an alloy having a fine crystal structure, preferably an alloy shown in the composition range of the present invention, a high magnetic permeability can be obtained. The coercive force can be reduced while maintaining the saturation magnetic flux density and the residual magnetic flux density. At the same time, it can be seen that if the manufacturing method of the present invention is applied, a soft magnetic alloy with little change over time can be provided if the heat is equal to or lower than the second heat treatment temperature.

[0090]

As described above, the method for producing an Fe-based soft magnetic alloy according to the present invention comprises Fe as a main component, Ti, Zr,
By subjecting the amorphous alloy containing one or more elements M and B selected from Hf, V, Nb, Ta, Mo, W, and Mn to the first heat treatment as described above, Fe ₃ B
Without precipitating a compound phase that deteriorates soft magnetic properties such as
A microcrystalline alloy mainly composed of Fe crystal grains having a fine bcc structure and having an average crystal grain size of 30 nm or less and containing an amorphous phase can be obtained. By forming a structure mainly composed of a crystal phase composed of fine crystal grains and a grain boundary amorphous phase existing at the grain boundary, excellent soft magnetic properties can be exhibited. By subjecting the microcrystalline alloy to a second heat treatment at a holding temperature of 100 ° C. or higher and lower than the holding temperature of the first heat treatment temperature, the soft magnetic properties are further improved, and the alloy is left at a high temperature for a long time. Even when the magnetic characteristics are not changed with time, it is possible to manufacture an Fe-based soft magnetic alloy of an Fe-based soft magnetic alloy which is suitable for a transformer or the like which can cope with processing during the manufacturing of a transformer or the like. Further, in particular, by setting the holding temperature at the time of performing the first heat treatment to 490 ° C. to 800 ° C., it is possible to preferably precipitate a microcrystalline phase mainly composed of bcc-Fe which contributes to soft magnetic characteristics. Therefore, it is possible to produce a soft magnetic alloy having a high magnetic permeability, a small coercive force and a small magnetostriction and exhibiting excellent soft magnetic properties.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a heat treatment pattern in the method for producing an Fe-based soft magnetic alloy of the present invention.

FIG. 2 is a graph showing an example of a heat treatment pattern in the method for producing an Fe-based soft magnetic alloy of the present invention.

FIG. 3 is a cross-sectional view of a part of an example of an apparatus suitably used for manufacturing the Fe-based soft magnetic alloy of the present invention.

[4] As a result of the coercive force of Fe _c Zr _d Nb _e B _f becomes the sample of the composition of the composition system similar to the composition system obtained by the present invention was measured with respect to the composition system from 0.034 to 0. 142 atomic% of the composition system with the addition of Zn in the range (Fe _c Zr _d Nb _e
FIG. 4 is a triangular composition diagram showing the result of measuring the coercive force of a sample having a composition of B _f ) _100-f Zn _f .

FIG. 5 is a triangular composition diagram showing the results of measuring the magnetic permeability (μ ′: real part of the magnetic permeability) at 1 kHz for a sample having the same composition as the sample whose test results are shown in FIG.

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

FIG. 7 is a triangular composition diagram showing a measurement result of a residual magnetic flux density (Br) of the above sample.

FIG. 8 is a triangular composition diagram showing the first crystallization temperature (T _x1 is the crystallization temperature of bccFe) of the previous sample.

FIG. 9 shows the intermediate crystallization temperature (T _x1 ′) of the previous sample.
Is a triangular composition diagram showing the crystallization temperature of the compound phase).

FIG. 10 shows the second crystallization temperature (T
_x2 is a triangular composition diagram showing the crystallization temperature of the compound phase).

FIG. 11 is a triangular composition diagram showing ΔT _x represented by T _x2 −T _x1 in the above sample.

FIG. 12 shows a composition system similar to the composition of the present invention and Z
It is a triangular composition diagram showing the crystal grain size of a sample of a composition system not containing n.

FIG. 13 shows a composition system similar to the composition of the present invention and Z
FIG. 4 is a triangular composition diagram showing magnetostriction (λs) of a sample of a composition system not containing n.

FIG. 14 is a diagram showing the Zn concentration dependence of the crystal grain size (D) of a composition-based alloy sample of the present invention to which Zn is added.

FIG. 15 is a view showing the Zn concentration dependence of the magnetostriction (λs) of the alloy sample of the present invention to which Zn is added.

FIG. 16 shows an alloy sample having a composition of Fe _85.75 Zr ₂ Nb ₄ B _8.25 containing Zn at 0.12 atomic% or 0.13 atomic%.
FIG. 9 is a diagram showing the results of measuring the iron loss of a sample to which atomic% is added by an AC magnetization characteristic measuring apparatus in comparison with the numerical values of a ribbon sample having a composition of Fe ₇₈ Si ₉ B ₁₃ of a comparative example.

FIG. 17 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the coercive force (Hc).

FIG. 18 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the magnetic permeability (μ ′).

FIG. 19 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the saturation magnetic flux density (B ₁₀ ) in an applied magnetic field of 10 Oe.

FIG. 20 is a view showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the residual magnetization (Br).

FIG. 21 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the average crystal grain size of a bcc-Fe phase.

FIG. 22 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the magnetostriction constant (λ _s ).

FIG. 23 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the heat treatment temperature (Ta) when the coercive force (Hc) is minimized.

FIG. 24 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the heat treatment temperature (Ta) when the magnetic permeability (μ ′) is maximized.

FIG. 25 shows the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic%, and the crystallization temperature (T _x1 ) of the bcc-Fe phase.
FIG.

FIG. 26 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the crystallization temperature (T _x2 ) of the FeB _x phase.

FIG. 27 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the crystallization temperature (T _{x1 ′} ) of a compound phase precipitated on a higher temperature side than the bcc-Fe phase. It is.

FIG. 28 is a diagram showing the relationship between the composition of a soft magnetic alloy in which the total amount of Zr and Nb is 6 atomic% and the crystallization temperature interval (ΔT _x ).

FIG. 29: Coercive force (iHc) of soft magnetic alloys of various compositions
FIG. 7 is a diagram showing the second heat treatment time dependency of FIG.

FIG. 30 is a diagram showing the second heat treatment time dependency of the magnetic permeability of soft magnetic alloys having various compositions.

[Explanation of symbols]

1 ... vacuum pump, 2 ... chamber, 3 ... cooling roll,
5 Nozzle, 6 Crucible, 7, 8 Gas supply source, 9
..Heating heater, 10 ... Molten metal.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akihiro Makino 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Kinshiro Takadate 1-7 Yukitani-Otsukacho, Ota-ku, Tokyo Alp (72) Inventor Akihisa Inoue 35-29 Kawachi Moto Hasekura, Aoba-ku, Aoba-ku, Sendai, Miyagi Prefecture 11-806 Kawauchi Housing Terms (reference) 5D093 AA01 AA03 AA06 BC18 JA12 JC01 5E041 AA11 AA19 CA02 CA05 HB11 NN01 NN06 NN17 NN18

Claims (17)

[Claims] 1. An alloy comprising Fe as a main component, Ti, Zr, Hf,
An amorphous alloy containing one or more elements M and B selected from V, Nb, Ta, Mo, W, and Mn is subjected to a first heat treatment to form a fine alloy having an average crystal grain size of 30 nm or less. bcc
After forming a microcrystalline alloy mainly composed of Fe crystal grains and containing an amorphous phase, a second heat treatment is performed at a holding temperature of 100 ° C. or more and not more than the holding temperature of the first heat treatment temperature. A method for producing an Fe-based soft magnetic alloy, which is characterized in that: 2. A holding temperature of the second heat treatment is 200 to 200.
2. The Fe according to claim 1, wherein the temperature is 400 ° C.
Manufacturing method of base soft magnetic alloy. 3. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the second heat treatment is performed while holding for 0.5 to 100 hours. 4. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the second heat treatment is carried out for 1 to 30 hours. 5. The first heat treatment is performed at 10 to 200 ° C. /
The method for producing an Fe-based soft magnetic alloy according to any one of claims 1 to 4, wherein the heating is performed at a rate of temperature rise for one minute. 6. The holding temperature of the first heat treatment is 500 to
The method for producing an Fe-based soft magnetic alloy according to any one of claims 1 to 5, wherein the temperature is 800 ° C. 7. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn, 0 ≦ a ≦ 0.1, 75 atomic% ≦ b ≦ 93 atomic%,
0.5 at% ≦ x ≦ 18 at%, 4 at% ≦ y ≦ 9 at%. 8. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y X z where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn,
X is Si, Al, Ge, Ga, 0 ≦ a ≦ 0.1,
75 atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18
Atomic%, 4 atomic% ≦ y ≦ 9 atomic%, and z ≦ 5 atomic%. 9. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y T t where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from W and Mn,
T is 1 selected from Cu, Ag, Au, Pd, and Pt.
A kind or two or more kinds of elements, and 0 ≦ a ≦ 0.1, 75
Atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, and t ≦ 5 atomic%. 10. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y T t X Z where, Z is Ni, 1 or two or more elements of Co, M is Ti, Zr, Hf, V, Nb, Ta, Mo ,
One or more elements selected from W and Mn,
T is 1 selected from Cu, Ag, Au, Pd, and Pt.
Species or two or more elements, X is Si, Al, Ge, Ga
0 ≦ a ≦ 0.1, 75 atomic% ≦ b ≦ 93 atomic%, 0.5 atomic% ≦ x ≦ 18 atomic%, 4 atomic% ≦ y ≦ 9
Atomic%, t ≦ 5 atomic%, and z ≦ 5 atomic%. 11. The method according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. Fe _b Zr _d Nb _{e B x} where 80 atomic% ≦ b, 5 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d / (d + e) ≦ 2.5 / 6,5 atomic% ≦ x ≦ 12.5 atomic%. 12. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b Zr d Nb e B x Zn f where, Z is Co, a or Ni,
a ≦ 0.05, 80 atomic% ≦ b, 1.5 atomic% ≦ d ≦ 2.
5 atomic%, 3.5 atomic% ≦ e ≦ 5.0 atomic%, 5 atomic% ≦
x ≦ 12.5 at%, 0.025 at% ≦ f ≦ 0.2 at%, 5.0 at% ≦ d + e ≦ 7.5 at%, 1.5
/6≦d/(d+e)≦2.5/6. 13. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. However _{Fe b Zr d Nb e B x} Zn f, 80 atomic% ≦ b, 1.5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦ e ≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 1
2.5 atomic%, 0.025 atomic% ≦ f ≦ 0.2 atomic%, and 5.0 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦
d / (d + e) ≦ 2.5 / 6. 14. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b Zr d Nb e B x Zn f M 'u where Z is Co, a or Ni,
M ′ is one or more elements selected from Cr, Ru, Rh, and Ir, a ≦ 0.05, 80 at%
≦ b, 1.5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦
e ≦ 5.0 atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.5 atomic%
025 atomic% ≦ f ≦ 0.2 atomic%, u ≦ 5 atomic%
5.0 atomic% ≦ d + e ≦ 7.5 atomic%, 1.5 / 6 ≦ d /
(D + e) ≦ 2.5 / 6. 15. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{Fe b Zr d Nb e B x} Zn f M 'u where M' is, Cr, Ru, Rh, is one or more elements selected from among Ir, 80 atomic% ≦ b, 1.
5 atomic% ≦ d ≦ 2.5 atomic%, 3.5 atomic% ≦ e ≦ 5.0
Atomic%, 5 atomic% ≦ x ≦ 12.5 atomic%, 0.025 atomic% ≦ f ≦ 0.2 atomic%, u ≦ 5 atomic%, and 5.0 atomic% ≦ d + e ≦ 7.5 atomic% 1.5 / 6 ≦ d / (d + e)
≤2.5 / 6. 16. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. _{(Fe 1-a Z a)} b B x M y Zn f where, Z is Co, a or Ni,
M is one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W; a ≦ 0.05, 80 at% ≦ b, 5 at% ≦ x ≦ 12.5
Atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.025 atomic%
≦ f ≦ 0.2 atomic%. 17. The method for producing an Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy is represented by the following composition formula. Fe _{b B x} M _y Zn _f where, M is Ti, Zr, Hf, V, Nb, Ta, Mo,
W is one or more elements selected from the group consisting of 80 atomic% ≦ b, 5 atomic% ≦ x ≦ 12.5 atomic%, 5 atomic% ≦ y ≦ 7.5 atomic%, 0.5 atomic% 025 atomic% ≦ f ≦ 0.2
Atomic%.