JPH07268566A - Production of fe-base soft-magnetic alloy and laminated magnetic core using the same - Google Patents

Abstract

PURPOSE:To produce an alloy having high saturation density and magnetic permeability and excellent in strength and thermal stability by specifying a composition and a crystalline structure, respectively, and also to obtain a laminated magnetic core having low core loss by using this alloy. CONSTITUTION:This alloy has a composition containing Fe as an essential component and also containing one or >=2 elements selected from the group consisting of Ti, Za, Hf, V, Nb, Ta, Mo, and W and B. Simultaneously, in this alloy, at least 50% or more of crystalline structure consists of fine crystalline grains of <=30nm average crystalline grain size, having body-centered cubic structure and the maximum strain is 1 at least at a heating of <=300 deg.C. Further, it is preferable that the composition of this alloy is the one to be represented by the formula. The laminated magnetic core can be produced by forming a molten metal of this alloy into a foil by rapid cooling, cutting this foil in a prescribed size, laminating the cut pieces of foil, heat-treating the resulting laminated foil at 400-700 deg.C to form fine crystalline phases in the inner part of the foil, coating the foil with resin, and then coiling it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft magnetic alloy used for a transformer, a choke coil, a magnetic head and the like and a method of manufacturing a laminated magnetic core using the soft magnetic alloy. And excellent soft magnetic properties.

[0002]

2. Description of the Related Art The characteristics generally required for soft magnetic alloys used for magnetic heads, transformers, choke coils, etc. are as follows: High saturation magnetic flux density. High magnetic permeability. Must have low coercive force. Must have low magnetostriction. It is easy to obtain a thin shape. Further, the magnetic head is required to have the following characteristics from the viewpoint of wear resistance in addition to the characteristics described above. High hardness. Therefore, when manufacturing a soft magnetic alloy or magnetic head,
From these viewpoints, material research has been conducted in various alloy systems. Conventionally, Sendust,
Crystalline alloys such as permalloy and silicon steel are used, and recently Fe-based and Co-based amorphous alloys have also been used.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the case of a choke coil, further miniaturization is required with the miniaturization of electronic devices, so that a magnetic material with higher performance is desired. Further, in the case of a magnetic head, a more suitable magnetic material for a high-performance magnetic head is desired in order to cope with a high coercive force of a magnetic recording medium accompanying a high recording density. However, although the sendust is excellent in soft magnetic properties, it has a drawback that the saturation magnetic flux density is as low as about 11 KG (1.1 T: Tesla), and permalloy is also saturated in an alloy composition having excellent soft magnetic properties. Magnetic flux density is about 8
It has a low defect of KG (0.8T), and is made of silicon steel (Fe-S).
Although the i-based alloy) has a high saturation magnetic flux density, it has the drawback of being inferior in soft magnetic properties.

On the other hand, among amorphous alloys, Co-based alloys are excellent in soft magnetic characteristics, but their saturation magnetic flux density is 10 KG (1
T), which is insufficient. Further, the Fe-based alloy has a high saturation magnetic flux density and can obtain 15 KG (1.5 T) or more, but the soft magnetic characteristics are insufficient. Also,
The thermal stability of amorphous alloys is not sufficient, and there are still unsolved aspects. Therefore, as described above, it is difficult to combine the high saturation magnetic flux density with the excellent soft magnetic characteristics.

Further, as a transformer alloy having a high saturation magnetic flux density and a low iron loss, as disclosed in JP-A-1-242757, a general formula (Fe _1-a M _{1 a} ) has been used. _100-klmn Cu _k Si _l
B _m M _{2 n} (where M ₁ is Co and / or Ni, M ₂ is at least one element selected from the group consisting of Nb, W, Ta, Mo, Zr, Hf and Ti, _a , _k , _l , _m , and _n are each atomic%, and 0 ≦ a ≦ 0.
3, 0.1 ≦ k ≦ 3, 0 ≦ l ≦ 17, 4 ≦ m ≦ 17, 10 ≦
l + m ≦ 28 and 0.1 ≦ n ≦ 5 are satisfied. ), An alloy having at least 50% of the structure of fine crystal grains, and having an average grain size of 1000 angstroms or less measured on the basis of the maximum size of the crystal grains is known.

The above-mentioned fine crystal alloy is disclosed in Japanese Patent Publication No. 4-439.
It was developed using a Fe-Si-B type amorphous alloy as a starting material as disclosed in Japanese Patent Publication No. 3 (U.S.P. No. 5,160,379). In the Fe-Si-B system alloy, the elements that amorphize the structure are Si and B,
The Fe content of the alloy having practically sufficient thermal stability is 70
~ 80 atomic%. This amorphous alloy is a conventional Fe-
It had a soft magnetic property superior to that of the Si-based alloy. The microcrystalline alloy according to the above patent application is Fe-
Fe-M ₁ -Cu- where Cu and element M are added to Si-B alloy
Si—B—M ₃ system, where the element M ₃ is Nb,
It is at least one element selected from W, Ta, Zr, Hf, Ti, and Mo. In this system alloy, Cu
It is said that the addition of Cu is an essential condition, and that the addition of Cu causes fluctuations in the amorphous material to generate fine crystal grains, thereby making the structure fine. Further, in the case of not containing Cu, it is difficult to reduce the size of crystal grains, a compound phase is easily generated, and the magnetic properties are deteriorated, which is described in the above-mentioned patent publication.

Further, in this type of alloy, Cu and Nb
The growth of crystal grains can be suppressed by the interaction with the. Therefore, since the growth of crystal grains cannot be suppressed only by adding Nb or Cu alone, it is said that the composite addition of Nb and Cu is essential. This is from p. 241 to p. 2 of the Japan Institute of Metals, Vol. 53, No. 2 (1989).
On page 48, it is described in the content published by the inventors of the above-mentioned patent application. From the composition diagram of FIG. 20 of Japanese Patent Publication No. 4-4393, it can be seen that low magnetostriction cannot be obtained when Si = 0 in the alloy of this system, and Si has an effect of reducing magnetostriction. So
The addition of Si is essential to reduce the magnetostriction.

The inventors of the present invention are developing soft magnetic materials by using materials having completely different components from the viewpoint of completely different from the above-mentioned conventional techniques. Among them, the above-mentioned sendust, permalloy, and silica are included. There is an Fe (Co, Ni) -Zr-based alloy found in Japanese Patent Publication No. 60-30734, which has been applied for a patent in view of conventional techniques such as raw steel. Since this Fe (Co, Ni) -Zr alloy is added with Zr, which has a large amorphous forming ability, even if the added amount of Zr is reduced, it can be made amorphous. Concentration 9
It can be 0% or more. Further, Hf can be used as an amorphous forming element similar to Zr. However, in this system, the Curie point of the alloy having a high Fe concentration is around room temperature, so that it was not a practical alloy as a magnetic core material.

Next, the inventors of the present invention can obtain a fine crystal structure having an average crystal grain size of about 10 to 20 nm by partially crystallizing the Fe-Hf type amorphous alloy by a special method. In 1980, he discovered "CONFERENCE ON
21 of "METALLIC SCIENCE AND TECHNOLGY BUDAPEST"
It is presented on pages 7 to 221. In view of the technology at the time of this announcement, it is suggested that in the Fe—Hf alloy, the structure may be refined without adding an element such as Cu. Although this mechanism is not clear, there are already structural fluctuations in the quenched state when forming an amorphous alloy, and these fluctuations act as sites for heterogeneous nucleation, and many uniform and fine nuclei are generated. It is considered to be a thing.

As described above, the Fe-Hf alloy does not show good magnetic characteristics in the amorphous state. However, considering that this alloy is refined without the need for non-magnetic additive elements, by using Fe-Hf type amorphous alloy as a starting material, a fine crystal alloy with a high Fe concentration which has never been obtained can be obtained. Therefore, it is expected that a new alloy having a higher saturation magnetic flux density than that of the Fe-Si-B-based fine crystal alloy will appear. Therefore, as a result of further research conducted by the present inventors, in order to suppress grain growth, it is necessary to enhance the thermal stability of the Fe-M-based microcrystalline alloy, and further, to prevent grain growth, the thermal stability that may become a barrier to grain growth is high. It is necessary to leave a stable amorphous phase at the grain boundaries. From such a point of view, as a result of research focused on B, which is an element that enhances the thermal stability of the amorphous alloy, Fe-
We have developed an M-B alloy.

Further, the inventors of the present invention have made repeated studies on alloys of this system and disclosed them in the above-mentioned Japanese Patent Publication No. 4393/1993 (USP No. 5,160,379). It has been found that excellent properties that cannot be obtained by the Fe-M ₁ -Cu-Si-B-M ₃ alloy are obtained. That is, the Fe-M ₁ -Cu-Si-B-M ₃ based alloy is 150
There is a property that it becomes brittle rapidly by heat treatment at ~ 200 ° C, and it is accompanied by heat treatment until it becomes a product, or it is partially heated to the above temperature with machining even if it is not subjected to heat treatment in particular Those involving steps, for example, a transformer manufactured by cutting a thin strip into an appropriate width and length, then winding it into a coil, and heat-treating it, a bonded magnetic head manufactured through a glass welding step, or It has a drawback that it cannot be applied to a laminated magnetic head or the like configured by laminating thin strips by press punching. Further, when a laminated core is produced by laser processing, the alloy is 1
There is a problem that this alloy cannot be applied to the production of a laminated core by laser processing because it becomes brittle at a low temperature of 50 to 200 ° C., and further there is a problem that it is not suitable for warm press processing performed at the above temperature or higher.

The object of the present invention is to have both a high saturation magnetic flux density and a high magnetic permeability, a high mechanical strength and a high thermal stability, and heat at the time of glass welding or heat of laser processing, or
It is an object of the present invention to provide a method for producing an excellent Fe-based soft magnetic alloy capable of withstanding heat of mechanical processing such as cutting or pressing and exhibiting excellent soft magnetic properties even after processing.

[0013]

In order to solve the above-mentioned problems, the invention as set forth in claim 1 contains Fe as a main component and Ti, Z
A body containing one or more elements M and B selected from the group consisting of r, Hf, V, Nb, Ta, Mo and W, and having at least 50% or more of the crystal structure having an average crystal grain size of 30 nm or less. It is composed of fine crystal grains with a centered cubic structure, and at least 30
The maximum strain is 1 at heat of 0 ° C. or lower.

In order to solve the above-mentioned problems, the invention according to claim 2 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. Fe _{b B x} M _y where, M is, Ti, Zr, Hf, V , Nb, Ta, Mo,
It is one or more elements selected from the group consisting of W and contains any of Zr, Hf and Nb, and the composition ratios b, x and y are b = 75 to 93 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%.

In order to solve the above-mentioned problems, the invention according to claim 3 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. _{(Fe 1-a Z a)} b B x M y However, Z is, Co, 1 kind or two kinds of Ni, M is Ti, Zr, Hf, V, Nb, Ta, Mo, from the group consisting of W The composition ratio is one or more selected elements and contains any one of Zr, Hf, and Nb.
a, b, x, y are a ≦ 0.2, b = 75 to 93 atom%, x =
The relations of 0.5 to 12 atom% and y = 4 to 9 atom% are satisfied.

In order to solve the above problems, the invention according to claim 4 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. Fe _{b B x} M _{y X
z} However, M is Ti, Zr, Hf, V, Nb, Ta, M
one or more elements selected from the group consisting of o and W, and contains any one of Zr, Hf, and Nb, and X is one or two of Cr, Ru, Rh, and Ir. More than one kind, and the composition ratios b, x, y, z are such that b = 75 to 93 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%, and z ≦ 5 atom%. Satisfied.

In order to solve the above-mentioned problems, the invention of claim 5 is such that the Fe-based soft magnetic alloy of claim 1 has a composition represented by the following formula. _{(Fe 1-a Z a)} b B x M y X z however, Z is Co, 1 kind or two kinds of Ni, M is T
i, Zr, Hf, V, Nb, Ta, Mo and W, which are one or more elements selected from the group consisting of:
Contains any one of Zr, Hf, and Nb, and X is Cr, R
u, Rh, Ir is one or more elements, and the composition ratios a, b, x, y are a ≦ 0.1, b = 75 to 93 atom%, x = 0.5 to 12 Atomic%, y = 4 to 9 atomic%, z ≦ 5
Satisfy the relationship of atomic%.

In order to solve the above-mentioned problems, the invention according to claim 6 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. Fe _{b B x} M _{y X} '
_t where M is Ti, Zr, Hf, V, Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing any of Zr, Hf, and Nb,
X ′ is one or more of Si, Al, Ge and Ga, and the composition ratios b, x, y and t are b = 75 to 93 atom%, x = 0.5 to 12 atom%, The relations of y = 4 to 9 atom% and t ≦ 4 atom% are satisfied.

In order to solve the above problems, the invention according to claim 7 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. _{(Fe 1-a Z a)} b B x M y X 't however Z is Ni, 1 kind or two kinds of Co, M is
Ti, Zr, Hf, V, Nb, Ta, Mo, W is one or more elements selected from the group consisting of Zr, Hf, Nb, and X'is Si. ，
One or more of Al, Ge, and Ga, and the composition ratios a, b, x, y, and t are a ≦ 0.2, b = 75 to 93 atomic%, x = 0.5 to 12 The relations of atomic%, y = 4 to 9 atomic% and t ≦ 4 atomic% are satisfied.

In order to solve the above-mentioned problems, the invention according to claim 8 is such that the Fe-based soft magnetic alloy according to claim 1 has a composition represented by the following formula. _{Fe b B x M y X z} X 't M ; however, Ti, Zr, Hf, V , Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing any of Zr, Hf, and Nb,
X is one or more of Cr, Ru, and Ir, and X ′.
Is one or more of Si, Al, Ge, and Ga, and the composition ratio b, x, y, z, t is b = 75 to 93 atom%,
It is assumed that the relations of x = 0.5 to 18 atomic%, y = 4 to 9 atomic%, z ≦ 5 atomic%, and t = ≦ 4 atomic%.

In order to solve the above problems, the invention of claim 9 is such that the Fe-based soft magnetic alloy of claim 1 has a composition represented by the following formula. _{(Fe 1-a Z a)} b B x M y X z X 't however Z may, Ni, 1 kind or two kinds of Co, M is T
i, Zr, Hf, V, Nb, Ta, Mo and W, which are one or more elements selected from the group consisting of:
Zr, Hf, or Nb is included, and X is Cr, Ru,
One or more of Ir, X'is Si, Al, G
e, Ga is one or more, and has a composition ratio a,
b, x, y, z, t are a ≦ 0.2, b = 75 to 93 atom%, x
= 0.5 to 18 atomic%, y = 4 to 9 atomic%, z ≦ 5 atomic%, and t = ≦ 4 atomic%.

In order to solve the above-mentioned problems, the invention according to claim 10 is produced by rapidly cooling the ribbon of the Fe-based soft magnetic alloy according to any one of claims 1 to 9 from molten alloy. Is cut into a predetermined size, further laminated, and then heat-treated to generate a fine crystal phase inside the ribbon, which is then coated with a resin and then wound.

In order to solve the above-mentioned problems, the heat treatment is performed at 400 to 700 ° C.

[0024]

In the Fe-based soft magnetic alloy having the composition according to the present invention, the maximum strain value does not decrease to a temperature range of 300 to 500 ° C. depending on the composition. This means that even if the alloy according to the present invention is partially heated to a temperature of 300 to 500 ° C., the alloy itself does not become brittle. Therefore, the alloy of the present invention does not become brittle even if the alloy of the present invention is heated wholly or partially by mechanical processing such as press working or laser processing or cutting processing. The alloy of the present invention can be applied to a transformer or a laminated magnetic head. Further, the Fe-based soft magnetic alloy of the present invention has a high saturation magnetic flux density,
Exhibits excellent soft magnetic properties with high magnetic permeability.

The present invention will be described in more detail below.
As a first example of the present invention alloy, represented by the composition formula Fe _{b B x} M _y, M is, Ti, Zr, Hf, V , Nb, T
a, Mo, W is one or more elements selected from the group consisting of a, Mo, W, and contains any one of Zr, Hf, Nb, the composition ratio b, x, y, b = 75 ~ 93 atom%, x
It is possible to use those satisfying the relations of 0.5 to 12 atom% and y = 4 to 9 atom%. As a second example of the present invention alloy, represented by the composition formula _{(Fe 1-a Z a)} b B x M y, Z is, Ni, represents one or two of Co, the composition ratio a, b, x, y are a ≦ 0.2, b = 75 to 93 atom%, x
It is possible to use those satisfying the relations of 0.5 to 12 atom% and y = 4 to 9 atom%.

As a third example of the alloy of the present invention, Fe _b B
_{It is represented by} a composition formula of _x M _y X _z , and X is Cr, Ru, R
One or more of h and Ir, and a composition ratio b,
As x, y, and z, those satisfying the relations of b = 75 to 93 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%, and z ≦ 5 atom% can be used. As a fourth example of the present invention _{alloy, (Fe 1-a Z a} ) is indicated by _b B _x M compositional formula of _y X _z, the composition ratio a, b, x, y, z is, a ≦ 0.1 , B = 75-9
3 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%, z
It is possible to use those satisfying the relation of ≦ 5 atomic%.

As a fifth example of the alloy of the present invention, Fe _b B
_x M _y X 'shown at _t a composition formula, X' is Si, A
1 or 2 or more of 1, Ge, and Ga, and the composition ratios b, x, y, and t are b = 75 to 93 atom%, x = 0.5 to 1
It is possible to use those satisfying the relations of 8 atomic%, y = 4 to 9 atomic%, and t ≦ 4 atomic%. As a sixth embodiment of the present invention _{alloy, (Fe 1-a Z a} ) b B x M y X ' is represented by a composition formula of _t, the composition ratio a, b, x, y, t is, a ≦ 0. 2, b = 75
It is possible to use those satisfying the relations of .about.93 atom%, x = 0.5-12 atom%, y = 4-9 atom%, and t ≦ 4 atom%.

As a seventh example of the alloy of the present invention, Fe _b B
_x M _{y X z X} 'is represented by a composition formula of _t, the composition ratio b, x, y,
As z and t, those satisfying the relations of b = 75 to 93 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%, z ≦ 5 atom%, t ≦ 4 atom% are used. be able to. An eighth embodiment of the present invention _{alloy, (Fe 1-a Z a} ) b B x M y X z
Is represented by a composition formula of X _'t, the composition ratio a, b, x, y, z, t is, a
≦ 0.2, b = 75 to 93 atomic%, x = 0.5 to 12 atomic%, y = 4 to 9 atomic%, z ≦ 5 atomic%, and t = ≦ 4 atomic%. Can be used.

Next, in the soft magnetic alloys of the above respective compositions,
The reason why the above composition is preferable will be described. B is inevitably added to the alloy having the above composition. It is considered that B has the effect of increasing the amorphous-forming ability of the soft magnetic alloy and the effect of suppressing the formation of the compound phase that adversely affects the magnetic properties in the heat treatment step, and therefore B addition is essential. Originally, Zr and Hf hardly form a solid solution with α-Fe, but by rapidly cooling the entire alloy having the above composition to amorphize it, Zr and Hf are supersaturated as a solid solution, and a heat treatment to be performed thereafter. By adjusting the solid solution amount of these elements to partially crystallize and precipitate as a fine crystalline phase, the soft magnetic characteristics of the obtained soft magnetic alloy can be improved and the magnetostriction of the ribbon can be reduced. Further, in order to precipitate the microcrystalline phase and suppress the coarsening of the crystal grains of the microcrystalline phase, it is considered necessary to leave the amorphous phase, which may hinder the crystal grain growth, at the grain boundary. . Furthermore, this grain boundary amorphous phase is the Zr, Hf, Nb discharged from α-Fe due to the rise of the heat treatment temperature.
Fe that deteriorates soft magnetism by forming a solid solution with M elements such as Fe
-It is considered that the production of M compounds is suppressed. Therefore F
It is important to add B to the e-Zr (Hf) -based alloy.

When the B content X is smaller than 0.5 at%,
Since the amorphous phase at the grain boundary becomes unstable, a sufficient addition effect cannot be obtained. Further, when X exceeds 12 atomic%, the tendency of BM-type and Fe-B-type borides to be generated becomes strong, and as a result, heat treatment conditions for obtaining a fine crystal structure are restricted, and good soft magnetic properties are obtained. Will not be obtained. The content of B is 1 in order to obtain a high saturation magnetic flux density of 1.5 T or more.
It is preferably 0 atomic% or less, but the amount of B is 10 to 1
If it is in the range of 8 atomic%, the electrical resistance of the alloy can be increased and the eddy current loss at high frequencies can be reduced.
It may be in the range of 0 to 18 atomic%. Thus, by adding an appropriate amount of B, the average crystal grain size of the fine crystal phase to be precipitated becomes 30 nm or less.

In the composition formulas of the soft magnetic alloys of the first to eighth examples, in order to easily obtain the amorphous phase, any one of Zr, Hf, and Nb having a particularly high amorphous forming ability is contained. There is a need. Further, Zr, Hf, and Nb can partially replace them with Ti, V, Ta, Mo, and W of the other 4A to 6A elements. In the alloy of the present invention, the M element is a relatively slow diffusion species, and the addition of the M element is considered to have the effect of reducing the growth rate of fine crystal nuclei, and is essential for the refinement of the structure. However, if the added amount Y of the M element is smaller 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 cannot be obtained. In the case of Fe-Hf-B type alloy, Hf =
The average crystal grain size at 5 atomic% is 13 nm, whereas when Hf = 3 atomic%, it becomes coarse at 39 nm. If the amount of Y exceeds 9 atomic%, the tendency of formation of MB-based or Fe-M-based compounds increases, good characteristics cannot be obtained, and the tape-like alloy after liquid quenching becomes brittle, and It becomes difficult to process it into a core shape. Therefore, the range of Y is set to 4 to 9 atom%.

In the composition formulas of the soft magnetic alloys of the second, fourth, sixth and eighth examples, b of Fe, Co and Ni contents is 93 atomic% or less. This is because when b exceeds 93 atom%, it becomes difficult to obtain an amorphous single phase by the liquid quenching method, and as a result, the structure of the alloy obtained after the heat treatment becomes non-uniform, resulting in high magnetic permeability. This is because it cannot be obtained. Further, in order to obtain the saturation magnetic flux density of 10 kG or more, it is more preferable that b is 75 atom% or more, so b is set to 75 to 93 atom%.

Among the above-mentioned additional elements, Nb and Mo have a small absolute value of free energy of oxide formation, are thermally stable, and are hard to oxidize during production. Therefore, when these elements are added, the manufacturing conditions are easy and the manufacturing cost is low, and the cost is also advantageous. When manufacturing the soft magnetic alloy by adding these elements, specifically, in the atmosphere while partially supplying an inert gas to the tip of the nozzle of the crucible used when quenching the melt. Can be manufactured in an atmosphere of air.

Although the reasons for limiting the alloying elements according to the present invention have been described above, platinum group elements such as Cr, Ru, Rh and Ir can be added to improve corrosion resistance other than these elements. is there. If these elements are added in an amount of more than 5 atom%, the saturation magnetic flux density is significantly deteriorated, so the addition amount must be suppressed to 5 atom% or less. Also,
If necessary, Y, rare earth element, Zn, Cd, Ga, I
n, Ge, Sn, Pb, As, Sb, Bi, Se, T
It is also possible to adjust the magnetostriction of the alloy by adding elements such as e, Li, Be, Mg, Ca, Sr and Ba. In addition, in the above alloy, inevitable impurities such as H, N, O, and S can be regarded as the same as the composition of the soft magnetic alloy used in the present invention even if they are contained to the extent that desired characteristics are not deteriorated. Of course.

In order to produce the above alloy, a liquid in which alloy raw materials are mixed so as to have the above composition and melted to obtain an alloy melt, and then the melt is jetted onto a rotating metal roll such as copper and rapidly cooled. Implement the quenching method. By this liquid quenching method, a ribbon-shaped ribbon in an amorphous state can be obtained. Once this thin strip is obtained, it can be cut into a required length or width or punched into a desired shape to be used for a transformer, a magnetic head, or the like.

Then, with respect to the processed ribbon, 500
It is preferable to perform a heat treatment of cooling after heating at ˜700 ° C. By this heat treatment, a fine crystalline phase is precipitated in the amorphous phase and magnetic characteristics are improved.

Next, an example of manufacturing a transformer core using a ribbon of the alloy having the above composition will be described. If an alloy ribbon of the above composition is prepared, this ribbon is shown in FIG.
It is wound around a reel 1 as shown in (a), and while the ribbon 2 is unwound from the reel 1, it is cut into a plurality of ribbons 4 having a predetermined width by a cutting device 3 such as a roller-shaped cutter. It is wound on the reel 5. In this example, one thin strip 2 is cut into three thin strips 4, so that the state shown in FIG. In this step, when the long ribbon 2 is continuously cut, the cutter portion of the cutting device 3 is in a heated state, and the cutting portion of the ribbon 2 is partially heated to a temperature of about 200 to 300 ° C. Since the alloy having the composition does not become brittle in the temperature range of 200 to 300 ° C., the ribbon is not damaged during cutting.

Next, as shown in FIG. 2 (a) or 2 (b), the thin strip 4 is taken out from the winding frame 5 and wound in a roll with an insulating tape to form a magnetic core body (toroidal core body) 6. To do. The insulating tape used here is provided for the purpose of preventing dielectric breakdown between layers during high voltage driving, and also for reducing heat generation by reducing eddy current loss. Resin film, resin tape, inorganic material film Or inorganic material tape or water glass with inorganic particles such as alumina, magnesia, boron nitride, silica sand, or quartz dispersed, or a resin tape coated with these inorganic particles or required after coating A product that is baked according to the above is appropriately used. As a resin material that constitutes the insulating tape, a solvent-type varnish tape in which an alkyd resin is dissolved in an organic solvent, a tape of a solvent-free varnish consisting of styrene monomer and unsaturated polyester resin, an acrylic resin, a polyester resin, an epoxy ester resin And the like. Instead of winding the ribbon 4 and the insulating tape at the same time, the ribbon 4 may be covered with an insulating layer and then wound. To cover the insulating layer on the ribbon 4, for example, the surface of the ribbon 4 is coated with inorganic particles by an electrophoretic method, by spraying, or by sputtering or vacuum deposition. A method or the like can be appropriately used. The insulating layer 2 can also be manufactured by injecting silica sand, quartz, etc., alone or in mixture, into the resin.

After the magnetic core body 6 is formed, the magnetic core body 6 is inserted into the heating furnace 7 as shown in FIG.
By heating to a temperature of 00 ° C., a fine crystalline phase is generated inside the ribbon 4. This heat treatment improves the soft magnetic properties of the soft magnetic alloy forming the ribbon and increases the hardness.

Next, the magnetic core body 6 is dipped in a resin liquid 9 as shown in FIG. 4 (a) to form a resin coating 10, and a winding 11 is wound as shown in FIG. 5 to wind the toroidal core shown in FIG. (Laminated magnetic core) 12 can be obtained. Further, in the above process, instead of coating with resin, the magnetic core body 6 is inserted into a storage case composed of the storage container 14 and the lid 15 as shown in FIG. A toroidal core may be manufactured.

When the toroidal core 12 is manufactured through the steps described above, even if there is a step in which heat is partially applied to the ribbon 2 such as a cutting process during the manufacturing process, the alloy thin film having the above composition is used. If it is a band, the toroidal core 12 can be manufactured without damaging the ribbon due to embrittlement. Since the toroidal core 12 thus obtained is mainly composed of the soft magnetic alloy having the above composition,
An extremely excellent saturation magnetic flux density of about 1.3 to 1.64 T (tesla) is exhibited, core loss in a high frequency region of about 100 kHz is reduced, heat generation is small, and characteristic deterioration does not occur. Therefore, it contributes to downsizing and weight saving of the toroidal core 12.

In the above example, the toroidal core 12 is manufactured by winding the ribbon 4. However, a ring may be manufactured by punching the ribbon 4 and the rings may be laminated to form a laminated magnetic core. . That is, a laminated magnetic core can be formed by forming a plurality of rings from the ribbon 4 by punching and laminating the rings with an insulating layer interposed therebetween. The material forming the insulating layer here may be the same as the material forming the insulating layer described above. Even in the laminated core of the structure of this example, since it is configured by laminating rings exhibiting excellent soft magnetic characteristics, it exhibits excellent soft magnetic characteristics and a small core loss,
Contributes to the reduction in size and weight of the magnetic core.

[0043]

[Examples] Molten alloy melts of various compositions were jetted onto the roll surface by Ar gas pressure from a nozzle arranged on a rotating copper roll, and rapidly cooled to form a plurality of alloy ribbons having a thickness of 20 to 23 μm. Obtained. The obtained alloy ribbon sample was Fe ₉₀
Zr ₇ B ₃ composition (thickness 20 μm) and Fe ₉₄ Nb ₇ B ₉
Composition (thickness 22 μm) and Fe _73.5 Si _13.5 B ₉ N
The composition is b ₃ Cu ₁ (thickness: 21 μm). Subsequently, in each sample, the ribbon was annealed at various temperatures, and then a bending test was performed to measure the maximum strain. In the bending process, two rods and a ribbon sample are used, and a ribbon arranged in parallel with the rod is sandwiched between the tips of the two rods, and the two rods are gradually brought close to each other to form the ribbon. The width between the end faces of the rod when the ribbon is broken and cut when bent in a mountain shape in this way is L
Then, the value of t / (L−t) is defined as the maximum strain (λf), where t is the thickness of the ribbon. The result is shown in FIG.

In FIG. 6, the sample having the maximum strain (λf) of 1 means that the two ribbons are bent without being cut until they come into contact with each other through the folded ribbons, and the value is larger than that. When it is lowered, it means that the ribbon is broken and cut in the middle of bending in a mountain shape. From the results shown in FIG. 6, the soft magnetic alloy sample having the composition of Fe ₉₀ Zr ₇ B ₃ and Fe ₈₄ Nb ₇ B ₉ according to the present invention has a temperature at which the maximum strain starts to decrease from 380 to 500 ° C. , 400-500 ℃
Means that it is less likely to become brittle even after annealing of
It was revealed that the comparative alloy sample having a composition of e _73.5 Si _13.5 B ₉ Nb ₃ Cu ₁ became extremely brittle by the annealing treatment at 100 to 200 ° C.

FIG. 7 shows the results of measuring the annealing temperature dependence of the maximum strain, hardness (Hv), and specific resistance (ρ) of a sample having a composition of Fe ₉₀ Zr ₇ B ₃ . From the results shown in FIG. 7, the alloy samples of this composition begin to improve in hardness and decrease in maximum strain when heat-treated at about 450 ° C. or higher. Therefore, during the manufacturing process, the alloy sample was processed at a temperature of 450 ° C. or lower. It is clear that even if something happens, it does not become brittle.

FIG. 8 shows the crystallization start temperature of the sample used in FIG. From the results shown in this figure, As-Quenche
Fe of the bcc structure can be obtained by heating to a temperature of about 550 ° C., regardless of whether the sample was d (unheated after quenching), heat-treated at 450 ° C. for 1 hour, or heat-treated at 470 ° C. for 1 hour. It is clear that heat is released due to the precipitation of Cu, which causes a change to a fine crystal structure.

FIG. 9 shows the results obtained by measuring the annealing temperature dependence of the maximum strain, hardness, and specific resistance of a sample (thickness 22 μm) having a composition of Fe ₈₄ Nb ₇ B ₉ . From the results shown in FIG. 9, the hardness of the alloy sample of this composition starts to be improved by the heat treatment at 350 ° C. or higher, and the maximum strain starts to decrease. Therefore, the alloy sample is processed at a temperature of 350 ° C. or lower during the manufacturing process. It is clear that things do not become brittle.

FIG. 10 shows Fe _73.5 Si _13.5 B ₉ Nb ₃ Cu ₁
It shows the results of measuring the maximum strain, hardness, and annealing temperature dependence of the specific resistance of a sample (thickness 21 μm) having the following composition. From the results shown in FIG. 10, the alloy sample of this composition has about 1
Hardness begins to improve and maximum strain begins to decrease by performing heat treatment at 50 ° C or higher.
It is clear that when it is processed at a temperature of 0 to 250 ° C. or less, it becomes brittle. This type of alloy becomes brittle at such temperatures because its solid solubility in Fe is extremely low.
It is considered that this is because it contains Si which tends to phase separate. That is, in the case of an alloy containing Fe and Cu, it is presumed that the tendency that the amorphous phase becomes non-uniform is more remarkable and thus embrittles.

Materials were prepared so as to have the compositions shown in Table 1 below, and this was melted at high frequency in a crucible with a nozzle to obtain a molten alloy, which was then transferred from a nozzle to a copper roll rotating at a high speed. A liquid quenching method of blowing out and quenching was performed to obtain an alloy ribbon having a thickness of 15 to 20 μm. The obtained ribbon was punched into an annular shape having an outer diameter of 10 mm and an inner diameter of 6 mm, and was subjected to a heat treatment of heating at 600 to 650 ° C. for 1 hour, and then insulating paper was attached to perform insulation treatment. A magnetic core is formed by stacking 20 disc bodies that have been subjected to this insulation treatment, winding is performed, and an AC magnetization test device (MM manufactured by Ryowa Electronics Co., Ltd.)
The core loss was measured using S0375). The results are shown in Table 1.

[0050]

[Table 1]

As is clear from the results shown in Table 1, the magnetic core according to the present invention exhibits an excellent saturation magnetic flux density in the range of 1.4 to 1.64 Tesla (T) and has a very small core loss at 100 kHz. Exhibited excellent characteristics.

[0052]

As described above, the present invention is a soft magnetic alloy having a special composition, and since the maximum strain is 1 at least at 300 ° C. or lower, it is subjected to heat treatment at about 100 to 300 ° C. Even if it is not embrittled, it can be machined and cut such as warm press and punching, and has a characteristic that it shows a high saturation magnetic flux density and a low core loss even after the processing.

Further, if a laminated magnetic core is formed by using the soft magnetic alloy having the above-mentioned special composition, even if the laminated magnetic core may be heated to 300 ° C. or lower in the process of manufacturing the laminated magnetic core,
Since it does not become brittle, it does not become brittle even if a laminated magnetic core is manufactured, which is obtained by mechanical processing such as warm pressing or punching, cutting, etc., and then winding. Magnetic flux density and low core loss are obtained. Further, even when compared with a magnetic core using an Fe-Si-B type amorphous alloy known to exhibit excellent soft magnetic characteristics, the laminated magnetic core according to the present invention has an equivalent excellent saturation magnetic flux. In addition to showing the density, the core loss is lower than the core loss of the Fe-Si-B based amorphous alloy. Therefore, according to the present invention, it is possible to provide a miniaturized and lightweight laminated magnetic core having a high saturation magnetic flux density with less loss in a high frequency range.

[Brief description of drawings]

FIG. 1 (a) is a perspective view showing a state where an alloy ribbon according to the present invention is being cut by a cutting device, FIG. 1 (b).
[Fig. 3] is a plan view showing a ribbon in the cut state.

FIG. 2 (a) is a side view showing a state in which a toroidal core body is manufactured by winding a thin strip after cutting,
FIG. 2B is an explanatory diagram showing the same state.

FIG. 3 is a cross-sectional view showing a state where the toroidal core body is heat-treated.

FIG. 4 (a) is a sectional view for explaining a state in which the toroidal core body after heat treatment is resin-coated, FIG.
(B) is an exploded perspective view showing a state in which the toroidal core main body after heat treatment is housed in a case.

FIG. 5 is a perspective view showing an example of a completed toroidal core.

FIG. 6 is a diagram showing a relationship between maximum strain and annealing temperature of an alloy sample according to the present invention.

FIG. 7 is a diagram showing a relationship among maximum strain, hardness, specific resistance, and annealing temperature of an alloy sample according to the present invention.

FIG. 8 is a diagram showing a crystallization temperature of an alloy sample according to the present invention.

FIG. 9 is a diagram showing the relationship among maximum strain, hardness, specific resistance and annealing temperature of another alloy sample according to the present invention.

FIG. 10 is a diagram showing a relationship among maximum strain, hardness, specific resistance and annealing temperature of an alloy sample of a comparative example.

[Explanation of symbols]

 2 ribbon 3 cutting device 4 ribbon 6 core body (toroidal core body) 11 winding 12 toroidal core

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuaki Hanya 1-7 Yukiya Otsuka-cho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Ken Masumoto 3-8-Uesugi, Aoba-ku, Sendai-shi, Miyagi Prefecture 22 (72) Inventor Akihisa Inoue Kawauchi Muzenchi, Aoba Ward, Sendai City, Miyagi Prefecture Kawauchi Housing 11-806

Claims (11)

[Claims] 1. Fe, as a main component, Ti, Zr, Hf,
V, Nb, Ta, Mo, W containing one or more elements M and B selected from the group consisting of V, Nb, Ta, Mo, W, and at least 50% or more of the crystal structure is a body-centered cubic structure having an average crystal grain size of 30 nm or less. An Fe-based soft magnetic alloy comprising fine crystal grains and having a maximum strain of 1 at a temperature of at least 300 ° C. 2. The Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. Fe _{b B x} M _y where, M is, Ti, Zr, Hf, V , Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing any of Zr, Hf, and Nb,
The composition ratios b, x and y are b = 75 to 93 atom%, x = 0.5 to 1
The relations of 2 atomic% and y = 4 to 9 atomic% are satisfied. 3. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{(Fe 1-a Z a)} b B x M y However, Z is, Co, 1 kind or two kinds of Ni, M is Ti, Zr, Hf, V, Nb, Ta, Mo, from the group consisting of W The composition ratio is one or more selected elements and contains any one of Zr, Hf, and Nb.
a, b, x, y are a ≦ 0.2, b = 75 to 93 atom%, x =
The relations of 0.5 to 12 atom% and y = 4 to 9 atom% are satisfied. 4. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. Fe _{b B x} M _{y X z} however, M is Ti, Zr, Hf, V, Nb, Ta, M
one or more elements selected from the group consisting of o and W, and contains any one of Zr, Hf, and Nb, and X is one or two of Cr, Ru, Rh, and Ir. More than one kind, and the composition ratios b, x, y, z are such that b = 75 to 93 atom%, x = 0.5 to 12 atom%, y = 4 to 9 atom%, and z ≦ 5 atom%. Satisfied. 5. The Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{(Fe 1-a Z a)} b B x M y X z however, Z is Co, 1 kind or two kinds of Ni, M is T
i, Zr, Hf, V, Nb, Ta, Mo and W, which are one or more elements selected from the group consisting of:
Contains any one of Zr, Hf, and Nb, and X is Cr, R
u, Rh, Ir is one or more elements, and the composition ratio a, b, x, y, z is a ≦ 0.1, b = 75 to 93.
Atomic%, x = 0.5 to 12 atomic%, y = 4 to 9 atomic%, z ≦
The relation of 5 atom% is satisfied. 6. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{Fe b B x M y X '} t where M is, Ti, Zr, Hf, V , Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing any of Zr, Hf, and Nb,
X ′ is one or more of Si, Al, Ge and Ga, and the composition ratios b, x, y and t are b = 75 to 93 atom%, x = 0.5 to 12 atom%, The relations of y = 4 to 9 atom% and t ≦ 4 atom% are satisfied. 7. The Fe-based soft magnetic alloy according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{(Fe 1-a Z a)} b B x M y X 't however Z is Ni, 1 kind or two kinds of Co, M is
Ti, Zr, Hf, V, Nb, Ta, Mo, W is one or more elements selected from the group consisting of Zr, Hf, Nb, and X'is Si. ，
One or more of Al, Ge, and Ga, and the composition ratios a, b, x, y, and t are a ≦ 0.2, b = 75 to 93 atomic%, x = 0.5 to 12 The relations of atomic%, y = 4 to 9 atomic% and t ≦ 4 atomic% are satisfied. 8. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{Fe b B x M y X z} X 't M ; however, Ti, Zr, Hf, V , Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing any of Zr, Hf, and Nb,
X is one or more of Cr, Ru, and Ir, and X ′.
Is one or more of Si, Al, Ge, and Ga, and the composition ratio b, x, y, z, t is b = 75 to 93 atom%,
It is assumed that the relations of x = 0.5 to 18 atomic%, y = 4 to 9 atomic%, z ≦ 5 atomic%, and t = ≦ 4 atomic%. 9. The Fe according to claim 1, wherein the Fe-based soft magnetic alloy has a composition represented by the following formula.
Base soft magnetic alloy. _{(Fe 1-a Z a)} b B x M y X z X 't however Z may, Ni, 1 kind or two kinds of Co, M is T
i, Zr, Hf, V, Nb, Ta, Mo and W, which are one or more elements selected from the group consisting of:
Zr, Hf, or Nb is included, and X is Cr, Ru,
One or more of Ir, X'is Si, Al, G
e, Ga is one or more, and has a composition ratio a,
b, x, y, z, t are a ≦ 0.2, b = 75 to 93 atom%, x
= 0.5 to 18 atomic%, y = 4 to 9 atomic%, z ≦ 5 atomic%, and t = ≦ 4 atomic%. 10. Fe according to claim 1.
A ribbon of the base soft magnetic alloy is produced by rapidly cooling it from a molten alloy, cutting this ribbon into a predetermined size, further laminating it, and then heat-treating it to generate a fine crystalline phase inside the ribbon. ,
A method of manufacturing a laminated magnetic core, characterized in that this is followed by resin coating and winding. 11. A method of manufacturing a laminated magnetic core, wherein the heat treatment is performed at 400 to 700 ° C.