JPH11131199A - Soft magnetic glass alloy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft magnetic glassy alloy having extremely enlarged temp. spacing in the supercooled liquid zone, having soft magnetism at room temp., and also having the possibility of production to a thickness larger than that of an amorphous alloy ribbon obtained by the conventional liquisol quenching process. SOLUTION: This alloy has a composition composed essentially of one or >=2 elements among Fe, Co, and Ni and also containing one or >=2 elements among Zr, Nb, Ta, Hf, Mo, Ti, and V and B. Further, in this alloy, the temp. spacing ΔTx in the supercooled liquid zone, represented by ΔTx=Tx-Tg (where Tx and Tg represent initial crystallization temp. and glass transition temp., respectively), is regulated to >=20K.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metallic glass alloy having soft magnetism and to an alloy having excellent soft magnetic properties.

[0002]

2. Description of the Related Art Certain types of multi-element alloys have conventionally been
It has a wide temperature range in the state of the supercooled liquid region before crystallization, these are metallic glass alloys (glassy all
oy). It is also known that this type of metallic glass alloy becomes a bulk amorphous alloy that is much thicker than a thin ribbon of an amorphous alloy manufactured by a conventionally known liquid quenching method. Conventionally, a thin ribbon of an amorphous alloy can be referred to as an Fe-PC-based amorphous alloy first manufactured in the 1960's, and manufactured in the 1970's (Fe, Co, N
i) -PB-based alloy, (Fe, Co, Ni) -Si-B-based alloy, 1
(Fe, Co, Ni) -M manufactured in the 980s
(Zr, Hf, Nb) alloy, (Fe, Co, Ni) -M
(Zr, Hf, Nb) -B alloys are known, but all of these alloys need to be rapidly cooled at a cooling rate of 10 ⁵ K / s, and the thickness of the manufactured alloys is 50
It was a ribbon having a thickness of not more than μm. In metallic glass alloys,
One having a thickness of several mm was obtained. As a metallic glass alloy of this type, Ln was used between 1988 and 1991.
-Al-TM, Mg-Ln-TM, and Zr-Al-TM (where Ln represents a rare earth element and TM represents a transition metal) have been discovered.

[0003]

However, none of these conventionally known metallic glass alloys has magnetism at room temperature, and in this respect, when viewed as a magnetic material, it is industrially large. There were restrictions. Therefore, conventionally, research and development of a metallic glass alloy which has magnetism at room temperature and can obtain a thick bulk material has been promoted.

[0004] Here, in the alloys of various compositions, even if the state of the supercooled liquid region is shown, the temperature interval ΔTx between these supercooled liquid regions, that is, the crystallization start temperature (Tx) and the glass transition temperature (Tg), In general, the difference of (Tx-Tg) is small, and in reality, it is poor in metallic glass forming ability and impractical. The existence of an alloy that has a temperature range and can form metallic glass by cooling,
It is of great interest in metallurgy since it is possible to overcome the limitation of the thickness of a conventionally known amorphous alloy as a ribbon. However, whether it can be developed as an industrial material depends on finding a metallic glass alloy that exhibits ferromagnetism at room temperature.

The present invention has been made in view of the above-mentioned circumstances, and has a very wide temperature interval in a supercooled liquid region, has soft magnetism at room temperature, and is smaller than an amorphous alloy ribbon obtained by a conventional liquid quenching method. It is an object of the present invention to provide a soft magnetic metallic glass alloy having a possibility of being manufactured thick.

[0006]

The soft magnetic metallic glass alloy according to the present invention contains one or more of Fe, Co, and Ni as main components, and contains Zr, Nb, Ta, Hf, and Mf.
At least one element selected from the group consisting of o, Ti, V, Cr, and W and B, and ΔTx = Tx−Tg (where Tx indicates a crystallization start temperature and Tg indicates a glass transition temperature). The temperature interval ΔTx of the supercooled liquid region represented by the equation is not less than 20K. In the present invention, the composition may include Zr, and ΔTx is 25K or more. Further, ΔTx may be not less than 60K and may be represented by the following composition formula. _{(Fe 1-ab Co a Ni} b) 100-xy M x B y where
0 ≦ a ≦ 0.29, 0 ≦ b ≦ 0.43, 5 atomic% ≦ x ≦ 2
0 atomic%, 10 atomic% ≦ y ≦ 22 atomic%, and M is Z
It is an element composed of one or more of r, Nb, Ta, Hf, Mo, Ti, V, Cr and W. Furthermore, the present invention is, 0.042 ≦ a ≦ 0.29,0.042 ≦ in the _{(Fe 1-ab Co a Ni} b) 100-xy M x B y a composition formula
It may be characterized in that a relationship of b ≦ 0.43 is satisfied.

Next, the present invention may be characterized in that ΔTx is 60K or more and is represented by the following composition formula. _{(Fe 1-ab Co a Ni} b) 100-xyz M x B y T z where, 0 ≦ a ≦ 0.29,0 ≦ b ≦ 0.43,5 atomic% ≦
x ≦ 15 atomic%, 10 atomic% ≦ y ≦ 22 atomic%, 0 atomic%
≦ z ≦ 5 atomic%, and M is Zr, Nb, Ta, H
f, Mo, Ti, V, Cr, W, one or more of the elements, T is Ru, Rh, Pd, Os, I
One or more of r, Pt, Al, Si, Ge, C, and P. Further, the present invention relates to the above (Fe
_{1-ab Co a Ni b)} 0.042 ≦ a ≦ 0.29,0.042 ≦ b ≦ 0.43 in the _{100-xyz M x B y T} z a composition formula
It may be the relationship that is made. Next, the element M is represented by (M ′ _1−c M ″ _c ), M ′ is one or two of Zr or Hf, and M ″ is Nb, Ta, Mo, Ti,
It may be an element composed of one or more of V, Cr and W, wherein 0 ≦ c ≦ 0.6. Further, in the above composition, c is 0.2 ≦ c ≦ 0.4.
And c may be in the range of 0 ≦ c ≦ 0.2.
Further, in the present invention, 0.042 ≦ a ≦ 0.25, 0.0
It may be characterized that 42 ≦ b ≦ 0.1. In the present invention, 427 to 627 ° C. is applied to the soft magnetic metallic glass alloy.
And heat treatment may be performed. Further, in the above composition, 50% or less of the element B may be replaced by C.

[0008]

Embodiments of the present invention will be described below with reference to the drawings. One of the soft magnetic metallic glass alloys according to the present invention contains one or more of Fe, Co, and Ni as main components, and further contains Zr, Nb, Ta, and H.
This is realized by a component system in which one or more of f, Mo, Ti, V, Cr, and W and a predetermined amount of B are added. One of the soft magnetic metallic glass alloy of the present invention, in the general formula can be expressed by _{(Fe 1-ab Co a Ni} b) 100-xy M x B y, in this formula, 0 ≦ a ≦
0.29, 0 ≦ b ≦ 0.43, 5 at% ≦ x ≦ 20 at%, 10 at% ≦ y ≦ 22 at% is preferable,
M is an element composed of one or more of Zr, Nb, Ta, Hf, Mo, Ti, and V. Further, in the above-mentioned component system, a temperature interval ΔTx of a supercooled liquid region represented by an equation of ΔTx = Tx−Tg (where Tx indicates a crystallization start temperature and Tg indicates a glass transition temperature) is 20K or more. Need. In the above-mentioned composition system, it is preferable that Zr is always contained and ΔTx is 25K or more. Also,
In the above-mentioned composition system, ΔTx is more preferably 60K or more. Further, the (Fe _1-ab Co _a Ni _b )
0.042 ≦ a ≦ 0 in _100-xy M _x B _y a composition formula.
29, it is preferable that 0.042 ≦ b ≦ 0.43.

Next, another soft magnetic metallic glass alloy according to the present invention has a general formula of (Fe _{1 -ab} Co _a Ni _b )
Is expressed in _{100-xyz M x B y T} z, in this formula,
0 ≦ a ≦ 0.29, 0 ≦ b ≦ 0.43, 5 atomic% ≦ x ≦ 2
0 atomic%, 10 atomic% ≦ y ≦ 22 atomic%, 0 atomic% ≦ z ≦
M is Zr, Nb, Ta, Hf, Mo,
An element composed of one or more of Ti, V, Cr, and W; T is Ru, Rh, Pd, Os, Ir, Pt, A
It is one or more of l, Si, Ge, C, and P. Further, the present invention relates to the above (Fe _1-ab Co _a Ni
_b) 0.042 ≦ the _{100-xyz M x B y T} z a composition formula
The relationship may be such that a ≦ 0.29 and 0.042 ≦ b ≦ 0.43.

Next, the element M is represented by (M ′ _{1 -c} M ″ _c ), wherein M ′ is one or two of Zr or Hf;
M ″ is an element composed of one or more of Nb, Ta, Mo, Ti, V, Cr and W, and 0 ≦ c ≦ 0.
6 may be used. Further, in the above composition, c may be in the range of 0.2 ≦ c ≦ 0.4, and c may be in the range of 0 ≦ c ≦ 0.2. Further, in the present invention,
0.042 ≦ a ≦ 0.25 and 0.042 ≦ b ≦ 0.1. In the present invention, the soft magnetic metallic glass alloy has a temperature ranging from 427 ° C. (700 K) to 627 ° C. (900 K).
The heat treatment may be performed in K). Those heat-treated at temperatures in this range exhibit high magnetic permeability. Note that, if quenched at the time of cooling after heating, the crystal phase precipitates and cannot be made amorphous. Therefore, the cooling rate after the heat treatment must be as low as possible, and treatment such as slow cooling or annealing after heating is preferable.
In the above composition, 50% or less of the atoms B may be replaced with C.

"Reasons for Composition Limitation" In the composition system of the present invention, the main components, Fe, Co and Ni, are elements that carry magnetism and are important for obtaining a high saturation magnetic flux density and excellent soft magnetic properties. Further, in a component system containing a large amount of Fe, ΔT
x tends to be large, and in a component system containing a large amount of Fe, C
By setting the o content and the Ni content to appropriate values, ΔTx
Can be set to 60K or more. Specifically, 5
In order to reliably obtain ΔTx of 0K to 60K, the value of a indicating the composition ratio of Co is set in the range of 0 ≦ a ≦ 0.29, and the value of b indicating the composition ratio of Ni is set in the range of 0 ≦ b ≦ 0.43. , Δ over 60K
In order to reliably obtain Tx, the value of a indicating the composition ratio of Co is set to the range of 0.042 ≦ a ≦ 0.29, and the value of b indicating the composition ratio of Ni is set to the range of 0.042 ≦ b ≦ 0.43. It is preferable that In order to obtain good soft magnetic properties within the above range, the value of a indicating the composition ratio of Co is set to 0.042.
≦ a ≦ 0.25 is preferable, and in order to obtain a high saturation magnetic flux density, the value of b indicating the composition ratio of Ni is more preferably in the range of 0.042 ≦ b ≦ 0.1. preferable.

M is Zr, Nb, Ta, Hf, Mo, T
It is an element composed of one or more of i, V, Cr and W. These are effective elements for forming an amorphous phase, and are preferably in the range of 5 atomic% to 20 atomic%. Further, in order to obtain high magnetic properties, the content is more preferably 5 at% or more and 15 at% or less. Among these elements M, Zr or Hf is particularly effective. Part of Zr or Hf can be replaced by an element such as Nb.
When Δc is in the range of 0.6, a high ΔTx can be obtained, but in particular, when ΔTx is 80 or more, 0.2 ≦ c
The range of ≦ 0.4 is preferred.

B has a high ability to form an amorphous phase. In the present invention, B is added in a range of 10 at% to 22 at%. Outside this range, if B is less than 10 atomic%, ΔTx disappears, which is not preferable.
If it is larger than this, it is not preferable because an amorphous phase cannot be formed. In order to obtain higher amorphous forming ability and better magnetic properties, it is more preferable that the content be 16 atomic% or more and 20 atomic% or less.

In the above composition system, R represented by T
u, Rh, Pd, Os, Ir, Pt, Al, Si, G
One or more of e, C, and P elements can be added. In the present invention, these elements can be added in a range of 0 atomic% to 5 atomic%. These elements are added mainly for the purpose of improving the corrosion resistance. If the content is out of this range, the soft magnetic properties deteriorate. If the ratio is out of this range, the amorphous forming ability is deteriorated, which is not preferable.

In order to produce a soft magnetic metallic glass alloy material having the above composition, for example, elemental elemental powder of each component is prepared,
These elemental elemental powders are mixed so as to be in the above composition range, and then this mixed powder is melted by a melting device such as a crucible in an inert gas atmosphere such as Ar gas to obtain a molten alloy having a predetermined composition. Next, this alloy melt is quenched by a single roll method, whereby a soft magnetic metallic glass alloy material can be obtained. The single-roll method is a method in which a molten metal is sprayed onto a rotating metal roll to quench the molten metal, thereby obtaining a ribbon-shaped metal glass in which the molten metal is cooled.

[0016]

EXAMPLE A pure alloy of Fe, Co, Ni and Zr and a pure boron crystal were mixed in an Ar gas atmosphere and arc-melted to produce a mother alloy. Next, this mother alloy was melted in a crucible and blown out from a 0.4 mm diameter nozzle at the lower end of the crucible into a copper roll rotating at 40 m / S in an argon gas atmosphere at an injection pressure of 0.39 × 10 ⁵ Pa. By performing the single roll method of quenching, the width is 0.4 to 1 mm,
Samples of metallic glass alloy ribbons having a thickness of 13 to 22 μm were produced. The obtained sample is analyzed by X-ray diffraction and differential scanning calorimetry (DSC), observed by a transmission electron microscope (TEM), and transmitted with a vibrating sample magnetometer (VSM) in a temperature range from room temperature to Curie temperature. Measure magnetic susceptibility and measure BH
A loop was obtained and the magnetic permeability at 1 kHz was measured.

FIG. 1 shows each of Fe ₆₀ Co ₃ Ni ₇ Zr
_{10 B 20, Fe 56 Co 7} Ni 7 Zr 10 B 20, Fe 49 Co 14 N
3 shows a DSC curve of a metal glass alloy ribbon sample having a composition of i ₇ Zr ₁₀ B ₂₀ and Fe ₄₆ Co ₁₇ Ni ₇ Zr ₁₀ B ₂₀ . By increasing the temperature of any of these samples, it is possible to confirm that a wide supercooled liquid region (supercooled zone) exists, and to crystallize by heating beyond the supercooled liquid region. Was revealed. The temperature interval ΔTx in the supercooled liquid region is represented by the equation ΔTx = Tx−Tg,
The value of Tx-Tg shown in FIG. 1 exceeds 60K in any of the samples, and is in the range of 64-68K. The substantially equilibrium state indicating the supercooled liquid region is 596 ° C. (869 K) to 632 ° C. slightly lower than the temperature at which crystallization due to the exothermic peak occurs.
(905K).

FIG. 2 shows (Fe _{1 -ab} Co _a Ni _b ) ₇₀ M ₁₀ B
Fe, Co and N with respect to the value of Tg in a composition system of ₂₀
FIG. 3 is a triangular composition diagram showing the content dependence of each i, and FIG. 3 is a graph showing the relationship between the value of ΔTx (= Tx−Tg) and F
FIG. 4 is a triangular composition diagram showing the dependency of each content of e, Co, and Ni on the triangular composition, and FIG. 5 shows the coercive force (H
Fig. 6 is a triangular composition diagram showing the dependence of Fe, Co and Ni on the value of c), and Fig. 6 is a graph showing the relationship between the magnetic permeability (μe) and the saturation magnetostriction (λs) in the same composition.
FIG. 4 is a triangular composition diagram showing the content dependence of Co, Ni and Co. As is clear from the results shown in FIG.
The value of ΔTx exceeds 25K in the entire range of the composition system of _1-ab Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ . FIG.
As can be seen from the figure, it was also clarified that, with respect to the value of Tg, increasing Co in the range of about 7 atomic% to about 50 atomic% monotonically increases Tg. On the other hand, as shown in FIG. 3, it was found that ΔTx had a large value in a composition system containing a large amount of Fe. In order to increase ΔTx to 60 K or more, the Co content was set to 3 atomic% or more and 20 atomic% or less. , Ni content is preferably at least 3 atomic% and at most 30 atomic%.

Incidentally, (Fe _1-ab Co _a Ni _b ) ₇₀ M ₁₀ B
_{In order to make the} Co content 3 atomic% or more in the composition formula ₂₀ , (Fe _{1 -ab} Co _a Ni _b ) is made 70 atomic%, so that the Co composition ratio a is 0.042 or more, and the Co content is 2
In order to reduce the content to 0 atomic% or less, the composition ratio a of Co becomes 0.29 or less. Similarly, to make the Ni content 3 atomic% or more, the Ni composition ratio b becomes 0.042 or more, and to make it 30 atomic% or less, the Ni composition ratio b becomes 0.43 or less.
As can be seen by comparing FIGS. 4, 5, 6 and 3, in the region where ΔTx is high, the saturation magnetization (Is), the coercive force (Hc), the magnetic permeability (μe) and the saturation magnetostriction (λs)
It can be seen that both are generally good.

FIG. 7 shows that the metallic glass alloy sample having the composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₁₀ B _{20 was} prepared at 660 ° C. (933
The result of performing X-ray diffraction analysis after annealing for 10 minutes at K) is shown. The annealing temperature of 660 ° C. is a temperature slightly higher than the temperature at which the sample of X = 7 shown in FIG. 1 showed an exothermic peak, and is considered to be a temperature at which crystallization can be performed by heat treatment at this temperature. In the obtained diffraction pattern, diffraction peaks of α-Fe, Fe ₃ B and Fe ₂ Zr were respectively recognized, and it was revealed that three types of crystal phases were precipitated and crystallized.

FIG. 8 shows that Fe _63-x Co _x Ni ₇ Zr ₁₀ B ₂₀ (x = 3,
(7, 14, 17 at%). The saturation magnetic flux density Bs was in the range of 0.91 to 0.96 T (tesla) without depending on the Co content. The coercive force Hc increased from 2.7 to 10 A / m in proportion to the Co content of 3 to 17 atomic%. The squareness ratio is
In the range of 0.32 to 0.45, Fe ₅₆ Co ₇ Ni ₇ Zr
The Curie temperature Tc of a sample having a composition of ₁₀ B ₂₀ is 294 ° C.
(567K). Also, from these soft magnetic properties, the heat treatment is performed at a glass transition temperature Tg (= 540.7 ° C., 8
It seems to be preferable to carry out at 480.7 ° C., which is 60 ° C. lower than 13.7K).

F after annealing at this temperature for 10 minutes
Samples saturation magnetic flux density Bs of the _{e 56 Co 7 Ni 7 Zr 10} B 20 composed composition 0.96T, the coercive force Hc is 2.41A / m, the squareness ratio Br / Bs was 0.4 to 0.6 . Further, Fe ₅₆ Co
₇ In the sample of Ni ₇ Zr ₁₀ B ₂₀ having a composition, 1 kHz
The magnetic permeability μe of the sample was 5100 for the sample in the quenched state at the time of manufacture, and 17700 for the sample after annealing. From this result, it can be seen that in the Fe-based composition system, better heat treatment can be obtained by performing heat treatment.

In the following, Fe₆₄Co_ThreeNi_ThreeZr_TenB₂₀, F
e₆₀Co_ThreeNi₇Zr_TenB₂₀, Fe₅₆Co₇Ni₇Zr_TenB
₂₀, Fe₄₉Co₁₄Ni₇Zr_TenB₂₀, Fe₄₆Co₁₇Ni₇
Zr _TenB₂₀Quenched state of the sample of each composition
Quenched state) and an annealing temperature of 427 ° C (700K).
477 ° C (750K), 527 ° C (800
K) and the respective saturation magnetic flux densities (Bs)
The measurement results of coercive force (Hc) and permeability at 1 kHz (μe)
Show.

○ Fe ₆₄ Co ₃ Ni ₃ Zr ₁₀ B ₂₀ Sample quenched 427 ° C. Annealed 477 ° C. Annealed 527 ° C. Bs 0.91 0.88 0.91 0.92 Hc 3.4 2.9 2.6 2.0 μe 4666 9639 12635 11882 ○ Fe ₆₀ Co ₃ Ni ₇ Zr ₁₀ B ₂₀ sample quenched 427 ° C. annealing 477 ° C. annealing 527 ° C. annealing Bs 0.92 0.93 0.92 0.93 0.93 Hc 2.72 .1 2.2 1.7 μe 4173 9552 11702 10896 ○ Fe ₅₆ Co ₇ Ni ₇ Zr ₁₀ B ₂₀ Sample quenched 427 ° C. Annealed 477 ° C. Annealed 527 ° C. Annealed Bs 0.95 0.95 0.96 0.96 0.94 hc 6.1 2.88 2.41 3.06 μe 5100 14260 17659 8121 ○ remains 427 ° C. Annie _{Fe 49 Co 14 Ni 7 Zr 10} B 20 samples quenched 477 ° C. Annealing 527 ° C. annealing Bs 0.94 0.93 0.93 0.93 Hc 9.9 3.7 3.37 5.526 ○ Fe 46 Co 17 Ni 7 Zr 10 B 20 remain 427 ° C. Annealing of the sample quench Annealed at 477 ° C. Annealed at 527 ° C. Bs 0.96 0.95 0.95 0.96 Hc 10.8 3.2 3.3 6.4

From the results of these measurements, in order to obtain a good value for the soft magnetic properties, the content of Co should be 3 atomic% or more and 17 atomic% or less, that is, the composition ratio a should be 0.042 or more and 0.25 or less. It is clear that is preferred.

FIG. 9 shows the quenched Fe _63-x Co ₇ Ni _x Zr ₁₀ B ₂₀ (x = 7,
The BH loop was determined for a sample having a composition of 14, 21, 28 atomic%). The saturation magnetic flux density Bs tended to decrease depending on the Ni content. Therefore, in order to obtain a high saturation magnetic flux density, it is understood that the Ni content is preferably set to 7 atomic% or less, in other words, the composition ratio b is set to 0.1 or less.

FIG. 10 is a graph showing the results of the same single roll method as in the previous embodiment, and the quenched Fe ₅₆ Co
₇ is obtained by seeking _{Ni 7 Zr 10-x Nb x} B 20 X -ray diffraction pattern of the sample (x = 0,2,4,6,8,10 atomic%) having a composition. Each of the obtained patterns is a typical broad pattern showing an amorphous state, and it is apparent that the samples having any compositions are amorphous.
FIG. 11 shows the results of obtaining DSC curves of the samples having the respective compositions shown in FIG. It can be seen that a wide supercooled liquid region that is in an equilibrium state exists in a temperature region lower than the exothermic peak temperature at which crystallization occurs in any sample of any composition.
However, in the samples with Nb contents of 8 atomic% and 10 atomic%, two exothermic peaks appear. Therefore, when adding Nb to this type of alloy, it is understood that the content is preferably set to 6 atomic% or less. Further, the temperature interval (ΔTx) of the supercooled liquid region of each composition sample shown in FIG.
In order to obtain the above, when a part of 10 atomic% of Zr is substituted with Nb, 2 atomic% or more and 4 atomic% or less, that is,
It can be seen that the composition ratio c is preferably set to 0.2 or more and 0.4 or less. The same applies to Hf.

FIG. 12 shows the glass of each composition sample shown in FIG.
Transition temperature (Tg), crystallization onset temperature (Tx), and supercooled liquid
4 shows the Nb content dependency of the temperature interval (ΔTx) of the region.
The glass transition temperature of the sample containing no Nb is 541 ° C.
(814K), crystallization onset temperature is 613 ° C (886K)
And the temperature interval in the supercooled liquid region is Nb content 2-4.
After showing the maximum in the range of atomic%, the Nb content increases and
It decreases monotonically. In addition, a sample containing no Nb
The temperature interval of the supercooled liquid region is 73K and contains Nb.
The maximum value of 85.2K is shown in the sample of 2 atomic%,₅₆
Co₇Ni ₇Nb_TenB₂₀45K even for samples with different compositions
The temperature intervals in the supercooled liquid region are shown. from this result,
When Nb is contained at about 8 to 10 atomic%, the supercooled liquid region
It is difficult to obtain amorphous due to small temperature interval
Become.

FIG. 13 shows Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb.
shows the results of X-ray diffraction analysis was annealed for 10 minutes at the temperature shown an exothermic peak with respect to metallic glass alloy samples of _x B ₂₀ a composition. In the figure, ● represents γ-Fe, ○ represents α-Fe.
Fe, ▲ is Fe ₂ Zr, △ is Fe ₇₆ Nb ₆ B ₁₈ , ■ is Co
₃ Nb ₂ B ₅ and □ indicate peaks of Ni ₈ Nb, and Δ indicates other exothermic peaks. In a sample having an Nb content of 2 to 4 atomic% and showing only one exothermic peak as shown in FIG. 11, heat treatment was performed at the exothermic peak temperature (1040 K), but γ-Fe, α -Fe, Fe ₂ Zr, Fe ₇₆ N
A peak of b ₆ B ₁₈ was observed. Nb content is 8, 10
As shown in FIG. 11, in the sample having two exothermic peaks as shown in FIG. 11, the sample heat-treated at temperatures of 883 K and 882 K near the first exothermic peak has γ-Fe
Is obtained, and the temperature of the second exothermic peak 1047
K, 1028K, γ-Fe, Co ₃
Peaks of Nb ₂ B ₅ and Ni ₈ Nb were observed.

From these results, in the sample having one exothermic peak, γ-Fe, α-Fe, Fe ₂ Zr, and Fe ₇₆ Nb ₆ B ₁₈ were precipitated from the amorphous phase during crystallization, and two exothermic peaks were formed. Γ-Fe precipitates from the amorphous phase at the first heat generation peak, and γ-Fe and C from the amorphous + α-Fe state at the second heat generation peak.
It was found that o ₃ Nb ₂ B ₅ and Ni ₈ Nb were precipitated.

FIG. 14 shows a rapidly cooled state of Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb _x B when manufactured by the single roll method.
_The BH loop of a sample having a composition of ₂₀ (x = 0, 2, 4, 6, 8, 10 at%) was obtained. Saturation magnetic flux density Bs
Is 0.92 T, N
0.55 T, Nb
Was 0.73 T in a sample to which 2 at% was added.
The coercive force Hc was 5.5 in the sample to which Nb was not added.
A / m, 4.2% in a sample added with 10 atomic% of Nb
A / m, 4.6 A in a sample added with 2 atomic% of Nb
/ M.

FIG. 15 shows Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb.
_x B _{20 (x} = 0,2,4,6,8,10 atomic%) made saturation magnetic flux density of 5 minutes annealed samples at a temperature of the sample and 527 ° C. After quenching composition (800 K) (Bs), coercive Magnetic force (H
c) Permeability at 1 kHz (μe), magnetostriction (λs)
Shows the Nb content dependence of The saturation magnetic flux density (Bs) is
Both the quenched state and the annealed sample decreased as Nb was added, with the sample not containing Nb being 0.9 (T) or more and the sample containing 2 atomic% of Nb being about 0.75 (T). The value of the magnetic permeability (μe) was 5031 for the sample in the quenched state without the Nb, 2228 for the sample containing 2 atomic% of Nb, and decreased to 906 for the sample containing 10 atomic% of Nb. did. However, by performing annealing, the magnetic permeability (μe) is significantly improved.
In a sample containing atomic%, a magnetic permeability (μe) of about 25000 can be obtained. Regarding the coercive force (Hc),
In the case of a quenched sample, a sample containing no Nb and a Nb
Are 50 A / m (= 0.62)
5 Oe). In particular, the sample having Nb of 2 atomic% or less shows a very good value of 5 A / m (= 0.0625 Oe). By performing the annealing, it is possible to obtain excellent coercive force (Hc) even in a sample containing 4 atomic% or more of Nb.

From the results shown in FIG. 13 and FIG. 15, in the alloy sample of this system, in order to obtain good soft magnetic characteristics, Nb is more preferably in the range of 0 to 2 atomic%. Recognize. Further, the magnetostriction does not depend much on the amount of Nb added. FIG. 16 shows Fe ₅₆ Co ₇ Ni ₇ Zr _10-x N
The Nb content dependency of the Curie temperature (Tc) of the sample after quenching with the composition of b _x B ₂₀ (x = 0, 2, 4, 6, 8, 10 at%) is shown together with the saturation magnetic flux density (Bs). The Curie temperature (Tc) shows the same Nb content dependency as the saturation magnetic flux density (Bs), and the Curie temperature (Tc) is 227 ° C. (500 K) when the Nb content is up to 8 atomic%.
As described above, it is understood that the material has high thermal stability.

FIG. 17 is a graph showing the relationship between Fe ₅₆ Co ₇ Ni ₇ Zr ₈ Nb ₂ B
The saturation magnetic flux density (Bs), the coercive force (Hc), and the magnetic permeability (μe) at 1 kHz of the sample having the composition of ₂₀ depend on the annealing temperature (holding time: 5 minutes). The structure of the alloy according to the annealing temperature is shown in the upper part of FIG. 17. The alloy of the present composition has a crystal structure (α-Fe + γ-Fe + Fe ₂ Zr + Fe ₇₆ N) from the amorphous single-phase state through the supercooled liquid region.
b ₆ to migrate to B _18). The saturation magnetic flux density (Bs) shows almost no dependence on the annealing temperature. Coercive force (H
In c), annealing at 527 ° C. (800 K) shows characteristics equal to or higher than that of the rapidly cooled state, but 627 ° C. (900 K).
The annealing at the above temperatures deteriorates. Magnetic permeability (μe)
About 427 ° C (700K) to 627 ° C (900K
By annealing in the range of K), it is possible to obtain characteristics higher than that of the rapidly cooled state. This temperature range includes the supercooled liquid region, and the optimum temperature range for annealing is desirably set to the supercooled liquid region and its vicinity.

FIG. 18 shows the dependence of the saturation magnetic flux density (Bs), the coercive force (Hc), and the magnetic permeability (μe) at 1 kHz on the annealing temperature (holding) of a sample having the composition of Fe ₅₆ Co ₇ Ni ₇ Nb ₁₀ B _20. Time 5 minutes). The structure of the alloy according to the annealing temperature is shown in the upper part of FIG. 18. The alloy of this composition has an amorphous single-phase state, a supercooled liquid region,
The crystal structure (γ-Fe
+ Ni ₈ Nb + Co ₃ Nb ₂ Ni ₅ ). The annealing temperature dependence of the saturation magnetic flux density (Bs), the coercive force (Hc), and the magnetic permeability (μe) is shown by Fe ₅₆ Co ₇ Ni ₇ Z shown in FIG.
It shows the same tendency as r ₈ Nb ₂ B ₂₀ alloy,
(700 K) to 627 ° C. (900 K), in other words, higher than the Curie point, indicating that it is effective to anneal in the supercooled liquid region and its vicinity.

When the Vickers hardness of the soft magnetic metallic glass alloy of the present invention was measured, it was found to show 1300 to 1500 Hv. From this, when the soft magnetic metallic glass alloy of the present invention is used as a core material of a magnetic head, it can be expected to provide a magnetic head having good wear resistance. In addition, the soft magnetic metallic glass alloy of the present invention can be expected to be used as a structural material or a tool.

Next, a test was performed to determine how thick a ribbon (ribbon) can be obtained in the Fe-based soft magnetic metallic glass alloy of the composition of the present invention. A pure metal of pure Fe, Co, Ni, Zr and Nb and a pure boron crystal were mixed in an Ar gas atmosphere, and arc-melted to produce a mother alloy. Next, this master alloy was melted in a crucible, and a single roll method was performed in which a copper roll rotating in an Ar gas atmosphere was blown out from a nozzle at the lower end of the crucible at a predetermined injection pressure to rapidly cool the copper roll, and the thickness was 20 to 195 μm. (Ribbon) was manufactured. The diameter of the nozzle hole as a nozzle is 0.4 to 0.7.
mm between the nozzle tip and the roll.
3-0.45mm, injection pressure 0.32-0.42kgf
/ Cm ² and the roll peripheral speed in the range of 2.6 to 41.9 m / s, a ribbon in the range of 20, 40, 100, 195 μm could be obtained. Note that the ribbon thickness could be easily increased by increasing the injection pressure and decreasing the roll peripheral speed. In addition, there was no problem in the production of ribbons of several tens of meters in any thickness sample.

FIG. 19 shows Fe ₅₆ Co obtained as described above.
₇ shows the X-ray diffraction pattern of each ribbon samples of Ni ₇ Zr ₄ Nb ₆ B ₂₀ a composition. According to the X-ray diffraction pattern shown in this figure, all the samples having a plate thickness of 20 to 195 μm have halo patterns at 2θ = 40 to 50 (deg), and have an amorphous single-phase structure. You can see that there is. From the above results, it has been clarified that in the composition system of the present invention, a ribbon having an amorphous single phase structure having a plate thickness in the range of 20 to 195 μm can be produced by the single roll method. Here, conventionally, in a general amorphous alloy, a quenching method using a rotating roll has a thickness of 20 to 40 μm.
Although it can be manufactured up to about m, it has been difficult to manufacture a thicker one. In other words, when an attempt is made to manufacture a ribbon having a thickness larger than this, there are problems such as breakage of the ribbon during production and crystallization. In contrast, in the composition system of the present invention, the temperature interval Δ
If Tx is large, a thick amorphous ribbon which cannot be obtained by the conventional composition system or manufacturing method can be obtained. This is an excellent characteristic peculiar to the alloy of the present invention having a temperature interval ΔTx of the supercooled liquid region which is so large as not found in the conventional material. Since such a thick ribbon can be made of an amorphous single phase, the space factor can be improved when forming a transformer or a magnetic head core or the like in a laminated or toroidal shape, and the substantial saturation magnetic flux density of the core can be improved. Can be increased. That is, when thin ribbons are laminated, an adhesive layer exists between the laminated ribbons, and the substantial space factor of the ribbon occupying the core is reduced. Further, when wound into a toroidal shape, a minute gap is formed between the wound ribbon of the inner layer and the ribbon of the outer layer. This can be avoided by using a ribbon.

Next, FIG. 20 shows a method according to the manufacturing method described above.
20mm thick and 15mm wide Fe₅₈Co₇N
i₇Zr_TenB₁₈Ribbon sample of different composition and Fe₅₆Co₇Ni
₇Zr _TenB₂₀Effective magnetic permeability using ribbon sample of different composition
2 shows the results of measuring the frequency dependence of the. The results shown in FIG.
From the results, it is clear that the soft magnetic glass alloy having the composition according to the present invention has MH
It can be seen that a sufficiently high effective magnetic permeability can be obtained up to the z band.
Also, the curve shown in FIG.
It can be determined that the characteristics are flat.

FIG. 21 shows that in a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ M ₁₀ B ₂₀ , the element M was changed to Ti, Zr, Hf, V, N
4 shows a DSC curve of a sample obtained by substituting each element of b, Ta, Mo, and W. It was found that there was a temperature difference between Tg and Tx in any of the sample compositions, and that a supercooled liquid region was present. The ΔTx of each sample shown in FIG. 21 was 46.5K when M = Ti, 73K when M = Zr, 82.2K when M = Hf, 28.2K when M = V, and M = V 44.9K in case of Nb, M = Ta
Is 56.5K, M = Mo is 33.9K, M =
In the case of W, it was 33.9K. FIG. 22 shows X-ray diffraction patterns of these samples. In each of the samples, a typical broad waveform indicating an amorphous phase was obtained. Turned out to be.

FIG. 23 is a graph showing the relationship between Fe ₅₆ Co ₇ Ni ₇ Zr ₈ M ₂ B ₂₀
In a sample having the following composition, the element M is represented by Ti, Zr, Hf,
3 shows a DSC curve of a sample obtained by substituting each element of V, Nb, Ta, Mo, and W. It was found that there was a temperature difference between Tg and Tx in any of the sample compositions, and that a supercooled liquid region was present. The ΔTx of each sample shown in FIG. 24 is 80.8K and M = H when M = Ti.
80.6K in case of f, 65.5K in case of M = V, M =
85.2K for Nb, 86.5K for M = Ta,
72.6K when M = Cr, 84.9K when M = Mo
It was 85.9K when K and M = W. FIG.
The X-ray diffraction pattern of each of these samples is shown in Fig. 10. A typical broad waveform indicating an amorphous phase was obtained in each of the samples, and it was found that each of the samples was in an amorphous single-phase state. found.

Next, in a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₈ M ₂ B ₂₀ , the element M was changed to Ti, Zr, Hf, V, N
The saturation magnetic flux density (T), the coercive force (Am ^-1 ), the effective magnetic permeability (μe: 1 kHz), and the Curie temperature (Tc) of the sample obtained by substituting each of the elements b, Ta, Mo, and W are obtained. The measurement results are shown below.

Composition Saturated magnetic flux density Coercive force Effective permeability Curie temperature (Bs) (Am ⁻¹ ) (μe: 1 kHz) Tc (° C.) M = Ti 0.82 1.9 12470 255 M = Hf 0.80 2. 2 9270 236 M = V 0.83 4.4 5210 257 M = Nb 0.75 1.1 25000 258 M = Ta 0.74 2.7 11970 230 M = Cr 0.75 1.9 10040 235 M = Mo 0.73 4.9 6490 217 M = W 0.70 5.7 8320 203 From these results, it was found that all the samples had excellent characteristics as soft magnetic materials.

FIG. 25 is a graph showing the relationship between Fe ₅₆ Co ₇ Ni ₇ Zr ₈ Hf ₂ B
When preparing ribbon samples having a composition of _20, the results obtained by preparing ribbon samples having different thicknesses by the same method as described above based on FIG. 19 and performing an X-ray diffraction test on each sample are shown. As shown in FIG. 25, it is possible to obtain a typical broad waveform indicating that the sample is FeCoNiZrHfB-based amorphous even in the case of the FeCoNiZrHfB-based sample, and to manufacture an amorphous ribbon from a very thick sample of 40 to 195 μm. There was found. In addition, in addition to this system, FeC
oNiZrTiB system, FeCoNiZrVB system, FeC
oNiZrNbB, FeCoNiZrTaB, Fe
CoNiZrCrB system, FeCoNiZrMoB system, F
Even if a sample of any composition system such as eCoNiZrWB system is produced, a broad waveform equivalent to that of FIG. 25 can be obtained, and even if a ribbon sample of any composition system is used, 40 to 19
It was found that thick amorphous samples in the range of 5 μm were obtained.

[0045]

As described above, according to the present invention, Fe, C
o, one or more elements of Ni as main components, and one or more elements of Zr, Nb, Ta, Hf, Mo, Ti, V, and B, and supercooling Since the temperature interval ΔTx of the liquid region is set to 20K or more, an amorphous soft magnetic metallic glass alloy exhibiting ferromagnetism at room temperature can be provided. Further, when ΔTx is 60K or more, (Fe _1-ab C
o _a Ni _b ) _100-xy M _x B _y , where 0 ≦ a ≦ 0.29, 0 ≦ b ≦ 0.43, 5 atom% ≦ x
≦ 15 atomic%, 16 atomic% ≦ y ≦ 22 atomic%, and if M is one or two or more of Zr, Nb, Ta, Hf, Mo, Ti, and V, the composition is strong at room temperature. An amorphous soft magnetic metallic glass alloy which exhibits magnetism and has excellent saturation magnetic flux density and excellent magnetic permeability can be provided. Further, when the soft magnetic metallic glass alloy of the present invention was measured for Vickers hardness, it was found to show 1300 to 1500 Hv. From this, when the soft magnetic metallic glass alloy of the present invention is used as a core material of a magnetic head, it can be expected to provide a magnetic head having good wear resistance. Further, the soft magnetic metallic glass alloy of the present invention can be expected to be used as a structural material, a tool, and the like.

Further, when ΔTx is 60K or more, (Fe _1-ab C
o _a Ni _b) shall be indicated by the _{100-xy M x B y T} z a composition formula, 0 ≦ a ≦ 0.29,0 ≦ b ≦ 0.43,5 atomic% ≦
x ≦ 15 atomic%, 16 atomic% ≦ y ≦ 22 atomic%, 0 atomic%
≦ z ≦ 5 atomic%, M is Zr, Nb, Ta, Hf, M
one or more of o, Ti, V, and Cr, and T is W, Ru, Rh, Pd, Os, Ir, Pt, Al, S
By using one or more of i, Ge, C, and P, an amorphous soft magnetic metallic glass alloy that exhibits ferromagnetism at room temperature and has excellent saturation magnetic flux density and magnetic permeability can be provided.

In the above-described composition system, good soft magnetic properties can be obtained by setting the value of a indicating the composition ratio of Co to 0.042 ≦ a ≦ 0.25, and the composition ratio of Ni can be reduced. By setting the value of b shown in the range of 0.042 ≦ b ≦ 0.1, a high saturation magnetic flux density can be obtained.

The element M is one of Zr and Hf.
It can be used in combination of an element M ′ consisting of one or two kinds and an element M ″, where M ″ is Nb, Ta, Mo, T
i, an element consisting of one or more of V,
When the element M is represented by (M ′ _1−c M ″ _c ), 0.2 ≦ c ≦
By setting the range to 0.6, a high ΔTx can be obtained, and by setting the range of 0 ≦ c ≦ 0.2, good soft magnetic characteristics and high saturation magnetic flux density can be obtained.

Next, a soft magnetic metallic glass alloy having a particularly high magnetic permeability can be obtained by subjecting the soft magnetic metallic glass alloys of the respective compositions to a heat treatment of heating at 427 to 527 ° C. and then cooling.

[Brief description of the drawings]

FIG. 1 Fe ₆₀ Co ₃ Ni ₇ Zr ₁₀ B ₂₀ , Fe ₅₆ Co ₇
Ni ₇ Zr ₁₀ B ₂₀ , Fe ₄₉ Co ₁₄ Ni ₇ Zr ₁₀ B ₂₀ , Fe
Is a diagram showing a _{46 Co 17 Ni 7 Zr 10 B} 20 becomes DSC curve of glassy alloy ribbon samples of each composition.

FIG. 2 is a triangular composition diagram showing the dependency of the contents of Fe, Co and Ni on the value of Tg in a composition system of (Fe _{1 -ab} Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ .

FIG. 3 is a triangular composition diagram showing the dependence of the contents of Fe, Co and Ni on the value of ΔTx (= Tx−Tg) in a composition system of (Fe ₁ -ab Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ It is.

FIG. 4 is a triangular composition diagram showing dependency of the contents of Fe, Co and Ni on the value of saturation magnetic flux density (Bs) in a composition system of (Fe _1-ab Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ . is there.

FIG. 5 is a triangular composition diagram showing dependency of the contents of Fe, Co and Ni on the value of coercive force (Hc) in a composition system of (Fe _1-ab Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ . .

FIG. 6 is a triangular composition showing dependency of the contents of Fe, Co and Ni on the magnetic permeability (μe) and magnetostriction (λs) in the composition system of (Fe _1-ab Co _a Ni _b ) ₇₀ M ₁₀ B ₂₀ FIG.

FIG. 7 is a diagram showing the results of X-ray diffraction analysis performed on a metallic glass alloy sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₁₀ B ₂₀ after annealing at 660 ° C. (933 K) for 10 minutes.

FIG. 8 shows a quenched state when manufactured by the single roll method.
Fe as it is_63-xCo _xNi₇Zr_TenB₂₀(X = 3,7,14,
17B shows a BH loop of a sample having a composition of 17 atomic%).
is there.

FIG. 9 shows a quenched state when manufactured by the single roll method.
Fe as it is_63-xCo ₇Ni_xZr_TenB₂₀(X = 7,14,2
FIG. 6 shows a BH loop of a sample having a composition of 1,28 atomic%).
It is.

FIG. 10 Rapid cooling state when manufactured by the single roll method
Fe as it is₅₆Co ₇Ni₇Zr_10-xNb_xB₂₀(X = 0,
X-ray diffraction pattern of a sample having a composition of 2, 4, 6, 8, and 10 atomic%).
It is a figure showing a turn.

FIG. 11 is a diagram showing a result of obtaining a DSC curve of each composition sample shown in FIG.

12 is a diagram showing the Nb content dependence of the glass transition temperature (Tg), the crystallization start temperature (Tx), and the temperature interval (ΔTx) of the supercooled liquid region of each composition sample shown in FIG.

FIG. 13 is a diagram showing the results of X-ray diffraction analysis after annealing a metallic glass alloy sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb _x B ₂₀ at a temperature at which an exothermic peak is exhibited for 10 minutes. It is.

FIG. 14 Rapidly cooled state when manufactured by the single roll method
Fe as it is₅₆Co ₇Ni₇Zr_10-xNb_xB₂₀(X = 0,
2,4,6,8,10 atomic%)
FIG.

FIG. 15: Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb _x B ₂₀ (x =
Nb content dependence of saturation magnetic flux density (Bs), coercive force (Hc), permeability at 1 kHz (μe), and magnetostriction (λs) of a sample having a composition of 0, 2, 4, 6, 8, and 10 atomic%) FIG.

FIG. 16: Fe ₅₆ Co ₇ Ni ₇ Zr _10-x Nb _x B ₂₀ (x =
It is a figure which shows the saturation magnetic flux density (Bs) and the Curie temperature (Tc) dependence of Nb content of the sample of the composition of 0,2,4,6,8,10 atomic%.

FIG. 17 shows the saturation magnetic flux density (Bs), coercive force (Hc), and 1 k of a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₈ Nb ₂ B _20.
FIG. 6 is a diagram showing the annealing temperature dependence of the magnetic permeability (μe) at Hz.

FIG. 18 shows a saturation magnetic flux density (Bs), a coercive force (Hc), and a saturation magnetic flux density (Bs) of a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Nb ₁₀ B _20.
FIG. 3 is a diagram showing the annealing temperature dependence of the magnetic permeability (μe) at kHz.

FIG. 19 is a view showing an X-ray diffraction pattern of each ribbon sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₄ Nb ₆ B ₂₀ .

FIG. 20 is a diagram showing the results of measuring the frequency dependence of the effective magnetic permeability of a ribbon sample having a composition of Fe ₅₈ Co ₇ Ni ₇ Zr ₁₀ B ₁₈ and a ribbon sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₁₀ B ₂₀ . It is.

FIG. 21 shows a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ M ₁₀ B ₂₀ in which the element M is represented by Ti, Zr, Hf, V, Nb, Ta,
D of a sample obtained by substituting each element of Mo and W
It is a figure which shows a SC curve.

FIG. 22 is an X-ray diffraction pattern of each sample shown in FIG.

FIG. 23 shows a sample having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₈ M ₂ B ₂₀ in which the element M is represented by Ti, Zr, Hf, V, Nb, and T.
It is a figure which shows the DSC curve of the sample obtained by substituting by each element of a, Mo, and W.

24 is an X-ray diffraction pattern of each sample shown in FIG.

FIG. 25 shows a thickness of a FeCoNiZrHfB-based ribbon sample of 40 μm, 100 μm, and 195 μm.
7 is an X-ray diffraction pattern of each sample m.

Claims (12)

[Claims] 1. One or more elements of Fe, Co, and Ni as main components, and Zr, Nb, Ta, Hf, M
At least one element selected from the group consisting of o, Ti, V, Cr, and W and B, and ΔTx = Tx−Tg (where Tx indicates a crystallization start temperature and Tg indicates a glass transition temperature). A soft magnetic metallic glass alloy, wherein the temperature interval ΔTx of the supercooled liquid region represented by the formula is 20K or more. 2. The soft magnetic metallic glass alloy according to claim 1, wherein Zr is always contained and ΔTx is 25K or more. 3. The soft magnetic metallic glass alloy according to claim 1, wherein ΔTx is 60 K or more and represented by the following composition formula. (Fe _1-ab Co _a Ni _b ) _100-xy M _x B _y where 0 ≦ a ≦ 0.29, 0 ≦ b ≦ 0.43, 5 atom% ≦
x ≦ 20 at%, 10 at% ≦ y ≦ 22 at%, and M
Are Zr, Nb, Ta, Hf, Mo, Ti, V, Cr, W
Is an element composed of one or more of the above. 4. The (Fe _{1 -ab} Co _a Ni _b ) _100-xy M
_{In the} composition formula xB _y , 0.042 ≦ a ≦ 0.29, 0.2.
4. The soft magnetic metallic glass alloy according to claim 3, wherein a relationship of 042 ≦ b ≦ 0.43 is satisfied. 5. The soft magnetic metallic glass alloy according to claim 1, wherein ΔTx is 60K or more and represented by the following composition formula. _{(Fe 1-ab Co a Ni} b) 100-xyz M x B y T z where, 0 ≦ a ≦ 0.29,0 ≦ b ≦ 0.43,5 atomic% ≦
x ≦ 20 at%, 10 at% ≦ y ≦ 22 at%, 0 at%
≦ z ≦ 5 atomic%, and M is Zr, Nb, Ta, H
f, Mo, Ti, V, Cr, an element composed of one or more of W, T is Ru, Rh, Pd, Os, Ir,
One or more elements of Pt, Al, Si, Ge, C, and P. 6. The (Fe _{1 -ab} Co _a Ni _b ) _100-xyz
In M _x B _y T _z a composition formula 0.042 ≦ a ≦ 0.2
9. The soft magnetic metallic glass alloy according to claim 5, wherein 0.04 ≦ b ≦ 0.43. 7. The element M is represented by (M ′ _{1 -c} M ″ _c ), wherein M ′ is one or two of Zr or Hf,
M ″ is an element composed of one or more of Nb, Ta, Mo, Ti, V, Cr and W, and 0 ≦ c ≦ 0.
The soft magnetic metallic glass alloy according to any one of claims 3 to 6, wherein 8. The composition ratio c is 0.2 ≦ c ≦ 0.4.
The soft magnetic metallic glass alloy according to claim 7, wherein: 9. The soft magnetic metallic glass alloy according to claim 7, wherein c representing the composition ratio is in the range of 0 ≦ c ≦ 0.2. 10. The composition ratios a and b are 0.04.
The soft magnetic metallic glass alloy according to claim 3, wherein the range is 2 ≦ a ≦ 0.25 and 0.042 ≦ b ≦ 0.1. 11. The soft magnetic metallic glass alloy contains 427 to
The soft magnetic metallic glass alloy according to any one of claims 1 to 10, wherein a heat treatment for cooling after heating at 627 ° C is performed. 12. The soft magnetic metallic glass alloy according to claim 3, wherein 50% or less of the element B is substituted with C.