JPH093608A - Iron-base soft-magnetic alloy and iron-base soft-magnetic alloy foil - Google Patents

Abstract

PURPOSE: To provide an Fe-base soft-magnetic alloy practically free from magnetostriction by preparing an alloy which has a bcc phase containing Si, etc., in solid-solution state and composed essentially of Fe and a B-containing amorphous phase and further contains Ti, etc., and in which the crystalline grain of the bcc phase is specified. CONSTITUTION: An alloy, which has a bcc phase (body-centered cubic crystal phase) containing one or >=2 elements among Si, Al, Ge, and Ga in solid-solution state and composed essentially of Fe and a B-containing amorphous phase and further contains one or >=2 elements among Ti, Zr, Hf, Nb, Ta, Mo, and W and in which fine crystalline grains of <=30nm average crystalline grain diameter comprise at least >=50% of the bcc phase structure, is prepared. By this method, the excellent Fe-base soft-magnetic alloy, practically free from magnetostriction as a whole and having high saturation magnetic flux density and superior magnetic permeability, can be obtained. This alloy is suitably used for transformer core.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Fe-based soft magnetic alloy used as a core material for transformers and the like, and a ribbon made of the same.

[0002]

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

[0003]

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

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

On the other hand, conventionally, 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 M5 _a ) 100 was used. _-xyzt Cu _x Si _y B
_z M6 _t (where M5 is Co and / or Ni, and M6
Is at least one element selected from the group consisting of Nb, W, Ta, Mo, Zr, Hf, and Ti, and the composition ratios a, x, y, z, and t are atomic%, and 0 ≦ a ≦ 0.3,
0.1 ≦ x ≦ 3, 0 ≦ y ≦ 17, 4 ≦ z ≦ 17, 10 ≦ y + z
≦ 28 and 0.1 ≦ t ≦ 5 are satisfied. ), A composition having at least 50% of the structure is composed of fine crystal grains, and the average grain size measured by the maximum dimension of the crystal grains is 1000 Å or less.

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 magnetic properties superior to those of Si-based alloys. The microcrystalline alloy according to the above patent application is Fe-S
Fe-M1-Cu-S with Cu and element M added to i-B alloy
i-B-M7 system, where element M7 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
Second of "METALLIC SCIENCE AND TECHNO-LOGY BUDAPEST"
It is presented on pages 17 to 221. In view of the technology at the time of this announcement, in the Fe-Hf alloy, Cu
It is suggested that the refinement of the structure can occur without adding such elements as. 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 type 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, it is necessary to enhance the thermal stability of the Fe-M (metal) -based microcrystalline alloy in order to suppress grain growth, and it may become a barrier to grain growth. It is necessary to leave a thermally stable amorphous phase at the grain boundaries, and from such a viewpoint, the research was advanced focusing on B, which is an element that enhances the thermal stability of the amorphous alloy. As a result, the present inventors have previously proposed a high saturation magnetic flux density Fe-based soft magnetic alloy that solves the above-mentioned problems.
No. 9 (Japanese Patent Application No. 2-108308)
We applied for a patent on the 24th of each month.

One of the alloys according to this patent application was a high saturation magnetic flux density characterized by having a composition represented by the following formula. (Fe _1-f Co _f ) _g B _h T1 _i T2 _j where T1 is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains either or both of Zr and Hf, and T2 is Cu, Ag, Au, Ni, Pd, or Pt. F is one or more elements selected from the group
≦ 0.05, g ≦ 92 atomic%, h = 0.5 to 16 atomic%, i
= 4 to 10 atom%, j = 0.2 to 4.5 atom%.

Another one of the alloys according to the above patent application is a high saturation magnetic flux density alloy characterized by having a composition represented by the following formula. Fe _g B _h T1 _i T2 _j where T1 is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains either or both of Zr and Hf, and T2 is Cu, Ag, Au, Ni, Pd, or Pt. 1 or 2 or more elements selected from the group consisting of g
≦ 92 atomic%, h = 0.5 to 16 atomic%, i = 4 to 10 atomic%, and j = 0.2 to 4.5 atomic%.

Further, the inventors of the present invention have disclosed, as an advanced alloy of the above-mentioned alloy, Japanese Patent Application Laid-Open No. 4-333546 (Japanese Patent Application No. 2-23).
No. 0135) In the specification, as of August 31, 1990, a patent application has been filed for an alloy having the following composition. One of the alloys according to this patent application was a high saturation magnetic flux density alloy characterized by having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x T _y However, Q is either or both of Co and Ni, and T
Is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W, and contains either or both of Zr and Hf, and a ≤
0.05, b ≦ 93 at%, x = 0.5-8 at%, y =
It is 4 to 9 atom%.

Further, another one of the alloys according to the above patent application is characterized by having a composition represented by the following formula. Fe _b B _x T _y However, T is Ti, Zr, Hf, V, Nb, Ta, Mo,
One or more elements selected from the group consisting of W, and containing either or both of Zr and Hf, b
≦ 93 at%, x = 0.5 to 8 at%, y = 4 to 9 at%. Next, as a result of intensive studies, the present inventors further proceeded with research on the soft magnetic alloy described in Japanese Patent Application Laid-Open No. 5-93249, and among the elements added to these systems, Si and Al The present invention has been completed by finding out that the solid solution of Fe, Ge and Ga in the bcc phase of Fe can adjust the magnetostriction.

The object of the present invention is to develop the soft magnetic alloy of the above-mentioned patent application so that the magnetostriction can be adjusted while maintaining the high saturation magnetic flux density and the high magnetic permeability, the core loss is small, and t
An object is to provide an Fe-based soft magnetic alloy that can reduce the value of an δ.

[0016]

In order to solve the above-mentioned problems, the Fe-based soft magnetic alloy according to claim 1 is made of Si, Al and G.
e, Ga, a bcc phase containing Fe as a main component in which one or more kinds are dissolved, and an amorphous phase containing B. Further, Ti, Zr, Hf, Nb, Ta , Mo, W
Bcc containing one or more elements M
At least 50% of the phase structure has an average crystal grain size of 30n
It is composed of fine crystal grains of m or less, and the magnetostriction is almost zero as a whole. In order to solve the above-mentioned problems, the Fe-based soft magnetic alloy described in claim 2 is the Fe-based soft magnetic alloy described in claim 1 having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta, M.
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and a, b, x, y and z showing composition ratios are a
= 0 to 0.2, b = 75 to 93 atom%, x = 0.5 to 18
Atomic%, y = 4 to 10 atomic%, and z = 5 atomic% or less.

In order to solve the above problems, the Fe-based soft magnetic alloy according to claim 3 is the Fe-based soft magnetic alloy according to claim 1 having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta, M.
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and M3 is Cu, Ag, Au, Pd, P
One or two or more elements out of t and Bi, and a, b, x, y, z, and d, which represent composition ratios, are a = 0 to 0.2,
b = 75 to 93 atom%, x = 0.5 to 18 atom%, y =
4 to 10 atom%, z = 5 atom% or less, d = 4.5 atom%
It is the following.

In order to solve the above problems, the Fe-based soft magnetic alloy according to claim 4 is the Fe-based soft magnetic alloy according to claim 1 having a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d M4 _e However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta. , M
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and M3 is Cu, Ag, Au, Pd, P
One or more elements out of t and Bi, M4
Is one or more elements of Cr, Ru, Rh, and Ir, and a, b, x, y, z, d, and
e is a = 0 to 0.2, b = 75 to 93 atom%, x = 0.
5 to 18 atomic%, y = 4 to 10 atomic%, z = 5 atomic% or less, d = 4.5 atomic% or less, and e = 5 atomic% or less.

In order to solve the above problems, the Fe-based soft magnetic alloy according to claim 5 has at least one of Ti, Nb, and Ta as M1 according to any one of claims 2 to 4. Element, and x = 6.5 to 18 atom%. The Fe-based soft magnetic alloy ribbon according to claim 7 is formed of the Fe-based soft magnetic alloy according to any one of claims 2 to 4. In order to solve the above problems, the Fe-based soft magnetic alloy ribbon according to claim 7 has a surface roughness R _{z of the} ribbon formed by the Fe-based soft magnetic alloy according to any one of claims 2 to 4. Is 4 to 8 μm, and the maximum surface roughness R _max is 6 to 1
It was set to 0 μm.

[0020]

When one or more of Si, Al, Ge and Ga form a solid solution in the bcc phase of Fe, magnetostriction can be reduced to almost zero. Further, it comprises the bcc phase and an amorphous phase containing B, and further comprises Ti, Zr, Hf,
One containing at least one element M of Nb, Ta, Mo and W, and at least 50% or more of the bcc phase structure composed of fine crystal grains having an average crystal grain size of 30 nm or less is magnetostrictive. In addition, it has a high saturation magnetic flux density and an excellent magnetic permeability, and thus is an excellent soft magnetic alloy, which is suitable for a transformer core.

In this type of Fe-based soft magnetic alloy,
(Fe _1-a Q _a ) _b B _x M 1 _y M 2 _z
Q is one or two of Ni and Co, and M
1 is one or more elements of Ti, Zr, Hf, V, Nb, Ta, Mo and W, M2 is Si,
One or more elements of Al, Ge, and Ga, a = 0 to 0.2, b = 75 to 93 atomic%, x = 0.5
Those having a range of -18 atom%, y = 4-10 atom% and z = 5 atom% or less have low magnetostriction and exhibit high saturation magnetic flux density and high magnetic permeability.

Further, in this type of Fe-based soft magnetic alloy, it is represented by a composition formula of (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d , and in addition to the above composition range, M3 is Cu , Ag,
One or two or more of Au, Pd, Pt, and Bi, which have d = 4.5 atomic% or less, have a low magnetostriction, a high saturation magnetic flux density, and a high magnetic permeability. Demonstrate. Furthermore, in this type of Fe-based soft magnetic alloy,
(Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d M4 _e It is shown by the composition formula, and in addition to the above composition range, M4 is Cr, Ru,
One or more of Rh and Ir, and e
= 5 atom% or less has a low magnetostriction and exhibits a high saturation magnetic flux density and a high magnetic permeability.

Further, as the element M1 of the Fe-based alloy,
One or more of Ti, Nb, and Ta, and x =
A material having a range of 6.5 to 18 atomic% also has a low magnetostriction and exhibits a high saturation magnetic flux density and a high magnetic permeability. Furthermore, a ribbon can be obtained from the Fe-based soft magnetic alloy, and by setting the surface roughness R _z of this ribbon to 4 to 8 μm and the maximum surface roughness R _max to 6 to 10 μm, a toroidal type transformer core can be obtained. It is suitable for use.

The present invention will be described in detail below. The Fe-based soft magnetic alloy of the present invention is obtained by quenching an amorphous alloy having the above composition or a crystalline alloy containing an amorphous phase from a molten metal, or by a vapor quenching method such as a sputtering method or a vapor deposition method. It can usually be obtained by carrying out the steps and a heat treatment step (annealing step) of heating and cooling those obtained in these steps to precipitate fine crystal grains. B is always added to the soft magnetic alloy of the present invention. It is considered that B has the effect of enhancing the amorphous form performance of the soft magnetic alloy and the effect of controlling the formation of the compound phase that adversely affects the magnetic properties in the heat treatment step, and therefore addition of B is essential. .

In the Fe-based soft magnetic alloy, in order to easily obtain an amorphous phase, Z having a high amorphous forming ability is used.
It preferably contains either r or Hf. Therefore, when these Zr and Hf are contained, the addition amount of B can be reduced, so that the B content can be set in a wide range of 0.5 to 18 atomic%. Zr and Hf are partially composed of Ti, V, Nb, and T among other 4A to 6A elements.
It can be substituted with one or more of a, Mo and W, and in that case, the same effect can be obtained. However, when an element other than Zr and Hf is added as one kind of the element M1, since the amorphous forming ability of the element other than Zr and Hf is low, the addition amount of B is in the range of 6.5 to 18 atomic%. It is preferable that Among these elements, Nb and Ta are metallic materials having a high melting point, are thermally stable, and are difficult to oxidize during manufacturing.

Therefore, when these elements are added in place of Zr and Hf, or when the above elements are increased by reducing Zr and Hf, the materials for which the inventors of the present invention have previously applied for patents The manufacturing conditions are easier and the manufacturing cost is lower than that mainly containing Hf or Zr, and the manufacturing cost is also advantageous. That is, in the alloy previously applied for a patent by the inventor of the present application, it was necessary to manufacture while paying attention to oxidation by supplying an inert gas in a vacuum atmosphere. The manufacturing conditions can be relaxed. Specifically, it becomes possible to manufacture in the atmosphere or in the atmosphere while partially supplying the inert gas to the tip of the nozzle.

Further, in the present invention, the element M to be added is
2 is one of Si, Al, Ge and Ga or 2
It is preferable that the content of the seeds is 5 atomic% or less. These are known as metalloid elements, but in the alloy of the present invention, these metalloid elements form a solid solution in the bcc phase (body-centered cubic phase) containing Fe as the main component. If the content of these elements exceeds 5 atomic%, the magnetostriction increases, the saturation magnetic flux density decreases, or the magnetic permeability decreases, which is not preferable.

Next, Cu, Ag, Au, Pd, and P are added as the element M3 to be added to the Fe-based soft magnetic alloy of the present invention.
One or more of t and Bi can be contained in an amount of 4.5 atomic% or less. Although the mechanism by which the addition of these elements improves the soft magnetic properties is not clear,
When the crystallization temperature was measured by a differential thermal analysis method, it was recognized that the crystallization temperature to which the above-mentioned elements such as Cu and Ag were added was slightly lower than that of the alloy without addition. It is considered that this is because the addition of the above elements made the amorphous material non-uniform, and as a result, the stability of the amorphous material decreased. When a non-uniform amorphous phase is crystallized, a large number of regions are likely to be partially crystallized, and non-uniform nuclei are generated. Therefore, the obtained composition is considered to have a fine grain structure.

From the above viewpoints, the same effect can be expected for the elements other than the above-mentioned elements that lower the crystallization temperature. Further, even in the case of an element whose solid solubility in Fe is extremely low, it is considered that there is a tendency for phase separation, and therefore microscopic composition fluctuation occurs due to heating, and the tendency that the amorphous phase becomes nonuniform becomes remarkable, It is considered to contribute to the refinement of the structure. However, if the added amount of elements such as Cu and Ag exceeds 4.5 atomic%, the magnetic properties such as soft magnetic properties and saturation magnetic flux density are deteriorated, which is not preferable.

Next, as the element M4 added to the Fe-based soft magnetic alloy of the present invention, one or more of Cr, Ru, Rh, and Ir can be contained in an amount of 5 atom% or less. These elements are added for the purpose of improving the corrosion resistance, and if the addition amount exceeds 5 atom%, the magnetic characteristics are deteriorated, which is not preferable.

Further, Fe, Ni, C in the alloy of the present invention
The amount of o is 75 to 93 atom%. This is because when b exceeds 93 atom%, high magnetic permeability cannot be obtained.
In order to obtain the saturation magnetic flux density of 10 kG or more, it is preferable that b is 75 atomic% or more.

On the other hand, a toroidal type magnetic core or the like can be obtained by winding the alloy ribbon of each composition obtained by the quenching method. In the case of a ribbon formed of the Fe-based soft magnetic alloy of each composition described above, a ribbon having small unevenness with a surface roughness R _{z of 4} to 8 μm and a maximum surface roughness R _max of 6 to 10 μm is obtained as described later. be able to. In addition, since this ribbon has few surface irregularities, even if the ribbon is wound to form a core for a toroidal type transformer core, the gap between the ribbons can be made small and per unit volume. Since the proportion of the soft magnetic material occupied can be increased, a suitable core with less loss can be obtained.

[0033]

EXAMPLES The reasons for limiting the composition of the soft magnetic alloy of the present invention will be described in detail below with reference to examples. The alloys shown in the following examples were prepared by the single roll liquid quenching method.
That is, molten metal is jetted onto the roll by the pressure of argon gas from a nozzle placed on one rotating steel roll, and rapidly cooled to obtain a ribbon. The width of the ribbon formed as described above is about 15 mm, and the thickness is about 20-40.
μm. Permeability is 10mm outer diameter after processing thin ribbon
m, ring-shaped with an inner diameter of 6 mm, or a width of 1 m
Measurement was performed by the inductance method using a rectangular sample having a length of m and a length of 60 mm. The measurement conditions of the effective magnetic permeability (μe) were 10 mOe and 1 kHz. Unless otherwise specified, the examples below show the magnetic characteristics after annealing at 600 ° C. to 700 ° C. for 1 hour and then annealing.

Fe _90-x Zr ₇ B ₃ Al _x composition Fe
A base soft magnetic alloy sample was prepared by the liquid quenching method, and the obtained sample was quenched, and the sample was heated to 600 ° C. and then gradually cooled at 3.6 ks for heat treatment. The magnetostriction (λs) was measured, and then the values of the saturation magnetic flux density (Bs) and the effective magnetic permeability (μe) of the heat-treated sample were measured. The respective measurement results are shown in FIG.

From the results shown in FIG. 1, Fe _90-x Zr ₇ B ₃ A
It is clear that when Al is added to the Fe-based soft magnetic alloy sample of the composition system of l _x , the magnetostriction increases as the amount of Al added increases, and when it is 5 atomic% or less, the magnetostriction value becomes close to zero. Is. Further, the magnetostriction becomes almost zero when the added amount of Al is 2 atomic%. That is, the magnetostriction can be reduced to 2.5 × 10 ⁻⁶ or less by setting the added amount of Al to 5 atomic% or less. Further, in order to lower the magnetostriction to the extent that it can be regarded as almost zero, it is clear that it is more preferable to set the amount of Al added in the range of 0 to 3 atomic%. this is,
It is considered that this is because Al was solid-dissolved in the bcc phase containing Fe as a main component, and the magnetostriction of the bcc phase gradually increased.

Further, from the results shown in FIG. 1, the saturation magnetic flux density decreases with an increase in the Al addition amount, and falls below 1.5 T (tesla) when the Al addition amount exceeds 5 atomic%. Therefore, it is clear that the Al addition amount needs to be set to 5 atomic% or less in order to set the saturation magnetic flux density to 1.5 T or more. Furthermore, since the effective magnetic permeability falls below 10,000 when the amount of Al added exceeds 10 atomic%, the effective magnetic permeability is 100%.
In order to achieve the value of 00 or more, the amount of Al added must be 10 atomic% or less. In view of the above results, it was determined in the present invention that the addition amount of Al is preferably 5 atomic% or less.

Next, regarding the magnetostriction, the saturation magnetic flux density, and the effective magnetic permeability of the sample having the composition of Fe ₈₈ Zr ₇ B ₃ Al ₂ and the sample having the composition of Fe ₈₉ Zr ₇ B ₂ Al ₂ , the heat treatment temperature dependence after manufacturing was examined. The measurement result is shown in FIG. From the results shown in FIG.
The magnetostriction is close to zero in the sample treated at the heat treatment temperature in the range of 550 ° C to 650 ° C, and it is clear that the saturation magnetic flux density is high and the value of the effective magnetic permeability is also high in this heat treatment temperature range. From the results shown in FIG. 2, to set the magnetostriction to near zero, the saturation magnetic flux density to around 1.5T or more, and the effective magnetic permeability to 10,000 or more, 550 to
It is clear that heat treatment in the range of 650 ° C. is preferable.

FIG. 3 shows the results of measuring the frequency dependence of core loss. As is clear from the results shown in FIG.
_In the alloy sample of the present invention showing the composition of ₈₃ Nb ₇ B ₉ Ga ₁ and Fe ₈₃ Nb ₇ B ₉ Al ₁ , the Fe-based amorphous alloy sample of the comparative example having the composition of Fe ₇₈ Si ₉ B ₁₃ or Ga, Al
It is apparent that the core loss is reduced at any frequency as compared with the comparative example sample having the composition of Fe ₈₄ Nb ₇ B ₉ to which is not added.

FIG. 4 shows Fe ₈₃ Nb ₇ B ₉ X ₁ (X = Ge, G
a, Al) and the sample of composition Fe ₈₄ Nb ₇ B ₉ to which the element X is not added, the frequency of μ ′ (permeability (real part)) and tan δ (dielectric loss tangent). The result of measuring the dependence is shown. As is clear from FIG. 4, the value of μ ′ is improved in the sample to which Ga and Ge are added. Also, the value of tan δ is reduced in a wide frequency range for the sample to which Al is added, and G
The samples with a and Ge added are also reduced in the low frequency region. From the above, Ge, Ga, Al
It is clear that the value of μ ′ can be improved and the value of tan δ can be reduced by adding

FIG. 5 shows the effective permeability (μe) and the saturation magnetic flux density (μe) when the Si content of the alloy sample having the composition of Fe _{90 -x} Zr ₇ B ₃ Si _x is changed in the range of 0 to 15 atomic%. B
s) and the value of magnetostriction (λs) are shown. As is clear from FIG. 5, in the sample heat-treated at 600 ° C., the Si content was 3
Magnetostriction becomes zero near atomic%, and even if the Si addition amount is increased, the magnetostriction does not increase, but when the Si addition amount exceeds 5 atomic%, the magnetic permeability is 10,000 and the saturation magnetic flux density is 1.
It is less than 5T, which is not preferable. Therefore, in order to obtain almost zero magnetostriction, high saturation magnetic flux density, and high effective magnetic permeability, the amount of Si added is preferably 5 atomic% or less, and more preferably 2 to 5 atomic%. Is clear.

FIG. 6 shows Fe ₈₆ Zr ₇ B ₃ Si ₄ , Fe ₈₇ Zr _7
3 shows changes in magnetic permeability, saturation magnetic flux density, and magnetostriction due to heat treatment in a sample of the present invention having a composition of B ₂ Si ₄ . FIG.
As is clear from the results shown in (1), a magnetostriction of almost zero, a saturation magnetic flux density of 1.5 T or more, and a magnetic permeability of 10,000 or more can be obtained at a heat treatment temperature in the range of 550 to 650 ° C. As in the above measurement results, the magnetostriction of the Fe-based soft magnetic alloy in the present invention becomes zero because Al, Si, G
It is considered that this is because the addition of semimetal elements such as a and Ge reduces the magnetostriction of the bcc phase of the Fe main component that occupies most of the structure to almost zero. As a result, when the soft magnetic alloy of the present invention is used for a magnetic core or the like, it is possible to prevent deterioration of soft magnetic characteristics due to resin molding. Further, when the soft magnetic alloy of the present invention is manufactured by the liquid quenching method, an alloy to which elements such as Al, Si, Ga and Ge are added has the same blowing temperature as that of an alloy to which these elements are not added. When manufactured, there is little deterioration of the nozzle, and there is a feature that the replacement of the nozzle is small. Therefore, in the case of mass production, the number of man-hours can be reduced by reducing the chance of nozzle replacement, and the manufacturing cost can be reduced.

FIG. 7 shows the amount of Si added to the surface roughness (R _z ) and the maximum surface roughness (R _max ) in the case where the alloy sample ribbon of the composition Fe _{90 -x} Zr ₇ Si _x B ₃ was manufactured by the quenching method. The result of having measured the influence of is shown. Surface roughness is JIS
The result of measuring the 10-point average roughness defined by B'0601 by a stylus type surface roughness meter is shown, and the maximum surface roughness is the maximum surface roughness measured by a stylus type surface roughness meter. As is clear from the results shown in FIG. 7, in the sample of this example, the surface roughness is in the range of 4 to 8 μm, the maximum surface roughness is in the range of 6 to 10 μm, and the unevenness is small and sufficiently small. It turned out to be. With such a small surface roughness value, when a thin strip is wound and coiled to manufacture a toroidal core or the like, a gap is less likely to be formed between the stacked thin strips. When processed, the density of the soft magnetic alloy existing per unit volume can be increased.

[0043]

As described above, the Fe-based soft magnetic alloy of the present invention exhibits a saturation magnetic flux density superior to that of conventional practical alloys, has a higher magnetic permeability than that of conventional practical alloys, and is 10000 depending on the composition. A magnetic permeability of more than 1.5 is easily obtained, a high saturation magnetic flux density of more than 1.5 T is exhibited, and a lower magnetostriction is exhibited. This is because one or more of Si, Al, Ge, and Ga can be dissolved in the bcc phase of Fe to form a solid solution, and the magnetostriction of the bcc phase, which occupies most of the structure, can be made almost zero. Further, the magnetostriction can be controlled according to the composition, and the magnetostriction can be made almost zero. Further, the alloy of the present invention can realize a core loss lower than that of the conventional alloy not only in the low frequency region but also in the high frequency region.
Since the value of nδ can be reduced and the loss can be reduced, it is possible to provide a core that can be used up to a high frequency range when used for the core.

In this type of Fe-based soft magnetic alloy, (F
e _1-a Q _a ) _b B _x M 1 _y M 2 _z
0 to 0.2, b = 75 to 93 atom%, x = 0.5 to 18 atom%, y = 4 to 10 atom%, z = 5 atom% or less, the magnetostriction is surely zero. It is possible to obtain a small value close to the above value, a saturation magnetic flux density exceeding 1.5 T, a magnetic permeability exceeding 10,000, and a small core loss and tan δ.

In this type of Fe-based soft magnetic alloy, the composition formula of (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d is shown and d = 4.5 at% or less. Even if it is, the magnetostriction can be surely set to a small value close to zero, and the saturation magnetic flux density exceeding 1.5T is exhibited, and the magnetic permeability is 1
It is possible to reliably obtain a core loss of more than 0000 and a small core loss and tan δ. Further, in this kind of Fe-based soft magnetic alloy, the composition formula represented by (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d M4 _e is shown, and the range of e = 5 atomic% or less is set. However, the magnetostriction can be surely reduced to a small value close to zero, the saturation magnetic flux density exceeding 1.5 T is exhibited, the magnetic permeability exceeds 10,000, and the core loss and tan δ are small.

As the element M1 of the Fe-based alloy,
One or more of Ti, Nb, and Ta, and x =
An Fe-based soft magnetic alloy with equivalent performance can be obtained even if the content is in the range of 6.5 to 18 atomic%. From the above, the soft magnetic alloy of the present invention is for a magnetic head for a transformer, a choke coil, or a magnetic recording medium having a high coercive force, which is required to be further downsized and improved in performance. It is suitable for use, and when it is used for these purposes, it has an effect of improving the performance and reducing the size and weight.

On the other hand, in the case of a ribbon formed of the Fe-based soft magnetic alloy of each composition described above, the surface roughness R _z is 4-8.
It is possible to obtain a thin ribbon having small irregularities with a maximum surface roughness R _max of 6 to 10 μm. In addition, since the ribbon of the present invention has few surface irregularities, even if the ribbon is wound to form a core for a toroidal type transformer core, the gap between the ribbons can be reduced and the unit volume can be reduced. Since the proportion of the soft magnetic material in the area can be increased, a suitable core with less loss can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing the influence of Al content on magnetostriction, saturation magnetic flux density, and effective magnetic permeability of an alloy sample having a composition of Fe _90-x Zr ₇ B ₃ Al _x according to the present invention.

FIG. 2 Dependence of heat treatment temperature on magnetostriction, saturation magnetic flux density, and effective permeability of alloy samples of composition Fe ₈₈ Zr ₇ B ₃ Al ₂ and alloys of composition Fe ₈₉ Zr ₇ B ₂ Al ₂ according to the present invention. FIG.

FIG. 3 Fe ₈₃ Nb ₇ B ₉ Ga ₁ and Fe ₈₃ N according to the present invention
b ₇ B ₉ Al ₁ showing an alloy sample and Fe ₇₈ Si ₉ B ₁₃
Comparative example amorphous alloy sample having the following composition and Fe ₈₄ Nb
Is a diagram showing the frequency dependence of the core loss of Comparative Sample having ₇ B ₉ a composition.

FIG. 4 shows Fe ₈₃ Nb ₇ B ₉ X ₁ (X = Ge,
Ga, shows a sample of Al) having a composition, the frequency dependence of the values of and tanδ of mu 'in the comparative example sample of Fe ₈₄ Nb ₇ B ₉ a composition.

FIG. 5 is a diagram showing influences of Si content on magnetostriction, saturation magnetic flux density and effective magnetic permeability of an alloy sample having a composition of Fe _90-x Zr ₇ Si _x B ₃ according to the present invention.

FIG. 6 shows heat treatment temperature dependence of magnetostriction, saturation magnetic flux density, and effective magnetic permeability of alloy samples having a composition of Fe ₈₆ Zr ₇ Si ₄ B ₃ and Fe ₈₇ Zr ₇ Si ₄ B ₂ according to the present invention. FIG.

FIG. 7 is a diagram showing the influence of Si content on the surface roughness and the maximum surface roughness of an alloy sample having a composition of Fe _90-x Zr ₇ Si _x B ₃ according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (71) Applicant 000010098 Alps Electric Co., Ltd. 1-7 Yukiya Otsuka-cho, Ota-ku, Tokyo (72) Inventor Akihisa Inoue Kawauchi Muzenchi, Aoba-ku, Sendai-shi, Miyagi 11-806 ( 72) Inventor Yoshihiro Miyauchi 2-11-8 Ginza, Chuo-ku, Tokyo Inside Nippon Electric Co., Ltd.

Claims (7)

[Claims] 1. A bcc phase containing Fe as a main component in which one or more of Si, Al, Ge, and Ga are in solid solution,
An amorphous phase containing B, and Ti, Z
r, Hf, Nb, Ta, Mo, W containing one or more elements M, and at least 50% or more of the bcc phase structure is composed of fine crystal grains having an average crystal grain size of 30 nm or less. An Fe-based soft magnetic alloy having a magnetostriction of almost zero as a whole. 2. The Fe-based soft magnetic alloy according to claim 1, which has a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta, M.
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and a, b, x, y and z showing composition ratios are as follows: a = 0 to 0.2, b = 75 to 93 Atomic%, x =
0.5-18 atom%, y = 4-10 atom%, z =
It is 5 atomic% or less. 3. The Fe-based soft magnetic alloy according to claim 1, which has a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta, M.
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and M3 is Cu, Ag, Au, Pd, P
One or two or more elements out of t and Bi, the composition ratios of a, b, x, y, z, and d are a = 0 to 0.2, b = 75 to 93 atomic%, x =
0.5 to 18 atom%, y = 4 to 10 atom%, z = 5 atom% or less, d =
It is 4.5 atomic% or less. 4. The Fe-based soft magnetic alloy according to claim 1, which has a composition represented by the following formula. (Fe _1-a Q _a ) _b B _x M1 _y M2 _z M3 _d M4 _e However, Q is one or two of Ni and Co, and M1 is Ti, Zr, Hf, V, Nb, Ta. , M
one or more of O and W, M2
Is one or more elements of Si, Al, Ge and Ga, and M3 is Cu, Ag, Au, Pd, P
One or more elements out of t and Bi, M4
Is one or more elements of Cr, Ru, Rh, and Ir, and a, b, x, y, z, d, and
e is a = 0 to 0.2, b = 75 to 93 atom%, x =
0.5 to 18 atom%, y = 4 to 10 atom%, z = 5 atom% or less, d =
It is 4.5 atomic% or less, and e = 5 atomic% or less. 5. The M1 is one of Ti, Nb, and Ta.
Fe-based soft magnetic alloy according to any one of claims 2 to 4, wherein the Fe-based soft magnetic alloy is one or two or more elements, and x = 6.5 to 18 atomic%. 6. An Fe-based soft magnetic alloy ribbon formed by the Fe-based soft magnetic alloy according to claim 2. 7. The surface roughness R _z of the ribbon formed of the Fe-based soft magnetic alloy according to claim 2 is 4 to 8 μm.
m, and the maximum surface roughness R _max is 6 to 10 μm.