JP3532392B2 - Bulk core - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bulk magnetic core provided with a soft magnetic metallic glass alloy used for a transformer, a choke coil, a magnetic sensor and the like.

[0002]

2. Description of the Related Art Conventionally, 50% Ni-Fe permalloy core, 80% Ni-Fe permalloy core, and silicon steel have been used as magnetic core materials for transformers, choke coils, magnetic sensors, and the like. However, the core made of these magnetic materials has a large core loss especially in a high frequency band,
In a frequency band of several tens of kHz or more, there is a problem that the temperature of the magnetic core is sharply increased and its use is difficult.

[0003] Recently, a core body formed by winding a ribbon of a Co-based amorphous alloy having a small core loss and a high squareness ratio, or a ribbon of an Fe-based amorphous alloy having a high saturation magnetic flux density and a high maximum magnetic permeability in a toroidal shape. Alternatively, a laminated magnetic core having a magnetic core body formed by laminating pieces punched into a predetermined shape is used.

[0004]

When winding or laminating the above-mentioned ribbons, a gap of about 3 μm is generated between adjacent ribbons due to unevenness of the surface of the ribbons. As described above, in the magnetic core formed by laminating the ribbons of the amorphous alloy, there is a problem that the core loss is increased due to the large leakage flux to the gap between the ribbons. Further, a method has been developed in which the raw material powder obtained by pulverizing the above-described ribbon is sintered and solidified to form a bulk, but at a relatively low temperature so that the raw material powder does not crystallize during sintering. Since it must be sintered, there is a problem that a high-density magnetic core cannot be obtained and core loss increases.

[0005] The present invention has been made to solve the above problems, and has as its object to provide a bulk magnetic core having a small core loss.

[0006]

In order to achieve the above object, the present invention employs the following constitution. The bulk magnetic core of the present invention contains one or more of Fe, Co, and Ni as main components, and includes Zr, Nb, Ta, Hf, Mo,
One or two or more elements of Ti and V and B, and an excess amount represented by a formula of ΔTx = Tx−Tg (where Tx indicates a crystallization start temperature and Tg indicates a glass transition temperature). The temperature interval ΔTx of the cooling liquid is 60 K or more , and
It is characterized by comprising a magnetic core body obtained by sintering a soft magnetic metallic glass alloy powder represented by a composition . (Fe _1-ab Co _a Ni _b ) _100-xy M _x B
_y, provided that 0.042 ≦ a ≦ 0.29, 0.042 ≦ b ≦
0.43, 5 at% ≦ x ≦ 20 at%, 10 at% ≦ y
≦ 22 atomic%, and M is Zr, Nb, Ta, Hf, M
Element consisting of one or more of o, Ti, and V
It is.

Further, the bulk magnetic core of the present invention, Fe, C
o, one or more elements of Ni as main components
And Zr, Nb, Ta, Hf, Mo, Ti, and V
One or two or more elements and B, ΔTx = Tx−
Tg (where Tx is the crystallization onset temperature and Tg is the glass transition
The temperature interval ΔT of the supercooled liquid represented by the formula
x is 60K or more and soft magnetic represented by the following composition
Equipped with a magnetic core body made of sintered metal glass alloy powder
Characterized in that that. (Fe _1-ab Co _a Ni _b ) _100-xyz M
_x B _y T _z where, 0.042 ≦ a ≦ 0.29,0.042 ≦ b ≦
0.43, 5 at% ≦ x ≦ 20 at%, 10 at% ≦ y
≦ 22 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, and M is Z
r, Nb, Ta, Hf, Mo, Ti, V
Or two or more elements, T is Cr, W, Ru, R
h, Pd, Os, Ir, Pt, Al, Si, Ge, C,
P is an element composed of one or more of P.

Further, the bulk magnetic core of the present invention is the bulk magnetic core described above, wherein the soft magnetic metallic glass alloy powder
Is heated at a rate of 10 ° C./min or less by the discharge plasma sintering method.
It is characterized by having a magnetic core body
Sign. Furthermore, in the present invention, Z
r or Hf may be included. Even better
Further, the bulk magnetic core of the present invention is the soft magnetic metal glass described above.
A core body formed by cooling and solidifying the molten alloy.
And features.

Next, the bulk magnetic core of the present invention is characterized in that 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,
It may be an element composed of one or more of Ti and V, wherein 0 ≦ c ≦ 0.6. Further, in the composition of the soft magnetic metallic glass alloy, c may be in a range of 0.2 ≦ c ≦ 0.4, and c may be in a range of 0 ≦ c ≦ 0.2. There may be a feature. Furthermore, the bulk magnetic core of the present invention is characterized in that, in the composition of the soft magnetic metallic glass alloy,
Is 0.042 ≦ a ≦ 0.25, b is 0.042 ≦ b ≦ 0.1
It may be characterized by being. The bulk magnetic core of the present invention may be characterized in that the soft magnetic metallic glass alloy is subjected to a heat treatment at 427 to 627 ° C. Further, in the composition of the soft magnetic metallic glass alloy, 50% or less of the element B may be replaced with C.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. The bulk magnetic core according to the present invention is realized in, for example, an annular shape. Such an annular bulk core forms a core body by sintering and molding a powder of a soft magnetic metallic glass alloy described later, or
By pouring a melt of a soft magnetic metallic glass alloy into a predetermined mold, cooling and solidifying to form a magnetic core body, and covering these magnetic core bodies with, for example, an epoxy-based resin or enclosing them in a resin case to insulate and protect them, A bulk core is obtained.

In order to realize an EI core type bulk core, an E-type core and an I-type core are prepared by sintering and molding a powder of a soft magnetic metallic glass alloy and joining them. This forms the magnetic core body. The EI core type bulk magnetic core can be obtained by coating the required portion of the magnetic core main body with, for example, an epoxy resin or enclosing the core in a resin case to insulate and protect the required portion.

FIG. 1 shows an example of an annular bulk magnetic core. This bulk magnetic core 1 has a hollow annular magnetic core main body storage case 2 made of a resin and is made of a soft magnetic metallic glass alloy described later. The core body 3 obtained by sintering the powder or pouring a molten metal of a soft magnetic metallic glass alloy into a predetermined mold and solidifying it by cooling is stored. Magnetic core storage case 2
Is preferably formed using a resin such as a polyacetal resin or a polyethylene terephthalate resin. Also, at two places on the bottom surface 2a of the magnetic core main body storage case 2,
An adhesive member 4 for stably fixing the magnetic core main body 3 and the magnetic core main body storage case 2 is applied. The number of positions where the adhesive member is applied is preferably in the range of 2 to 4 positions.
Epoxy resin, silicon rubber, or the like is used as the bonding member 4.

Next, a method of manufacturing the bulk magnetic core 1 according to the present invention by a plasma sintering method will be described. FIG. 2 shows a main part of one example of a spark plasma sintering apparatus suitable for manufacturing the bulk magnetic core 1 according to the present invention. An upper punch 12 and a lower punch 13 inserted into the die 11, a punch electrode 14 which supports the lower punch 13 and serves as one electrode when a pulse current to be described later flows, and a lower punch 12 is placed on the lower side. It is mainly composed of a punch electrode 15 which is the other electrode to be pressed and through which a pulse current flows, and a thermocouple 17 for measuring the temperature of the raw material powder 16 sandwiched between the upper and lower punches 12 and 13. Upper punch 12 and lower punch 1 described above
A mold corresponding to the shape of the magnetic core main body to be obtained is formed on the surface of each of 3 facing each other. Further, a main part of the above-described spark plasma sintering apparatus is housed in a chamber (not shown). This chamber is connected to a not-shown evacuation device and an atmosphere gas supply device,
The raw material powder (granules) 16 to be filled between the upper and lower punches 12 and 13 can be held in a desired atmosphere such as an inert gas atmosphere.

In order to manufacture the bulk magnetic core 1 using the spark plasma sintering apparatus having the above-described structure, a raw material powder for molding is prepared. The raw material powder 16 is prepared by melting a soft magnetic metallic glass alloy having a predetermined composition, which will be described later, by a casting method, or by a quenching method using a single roll or twin rolls, and further by a submerged spinning method or a solution extraction method. Alternatively, it can be obtained by a process of producing various shapes such as a bulk, a ribbon, a linear body, and a powder by a high-pressure gas atomization method, and a process of pulverizing and pulverizing a material other than the powder.

The soft magnetic glassy alloy used in the present invention, the temperature interval [Delta] T _x of the supercooled liquid alloy, 20K or more, 40K or more depending on the composition further has a significant temperature interval of more than 50K, ever It is completely unexpected from other alloys known from the findings of the above. Moreover, it also has excellent properties at room temperature for soft magnetism,
It is a completely new thing that cannot be seen in previous findings.

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 contains Zr, Nb, Ta, Hf, Mo, Ti,
This is realized by a component system in which one or more of V and B are added in a predetermined amount. 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, the temperature interval ΔTx of the supercooled liquid region represented by the formula of ΔTx = Tx−Tg (where Tx indicates a crystallization start temperature and Tg indicates a glass transition temperature) is 20K or more. Need that. In the above composition system, it is preferable that the composition always contains Zr or Hf and ΔTx is 25K or more. Further, in the above composition system, it is more preferable that ΔTx is 60K or more. Further, the (Fe
_1-ab Co _a Ni _b ) In the composition formula of _100-xy M _x B _y, it is preferable that 0.042 ≦ a ≦ 0.29 and 0.042 ≦ b ≦ 0.43.

Next, another soft magnetic metallic glass alloy according to the present invention has a general formula (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 ≦
5 atomic%, and M is Zr, Nb, Ta, Hf, Mo,
T is Cr, W, Ru, Rh, Pd, Os, Ir, Pt, A, which is an element composed of one or more of Ti and V.
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 ≦ In _{100-x -yz 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 ), and M' is one or two kinds of Zr or Hf.
Is an element composed of one or more of Nb, Ta, Mo, Ti, and V, and may be characterized in that 0 ≦ c ≦ 0.6. 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, 0.042≤b≤0.1. In the present invention, the soft magnetic metallic glass alloy may be heat-treated at 427 ° C. (700 K) to 627 ° C. (900 K). Those heat-treated at temperatures in this range exhibit high magnetic permeability. In the above composition, 50% or less of the atom B is C
May be substituted.

"Reason for composition limitation" In the composition system of the present invention,
Fe, Co and Ni, which are main components, are elements responsible for magnetism, and are important for obtaining high saturation magnetic flux density and excellent soft magnetic characteristics. Specifically, in order to reliably obtain ΔTx of 50K to 60K, the value of a indicating the composition ratio of Co is set to 0 ≦ a
≦ 0.29, the value of b indicating the composition ratio of Ni is set to 0 ≦ b ≦ 0.4.
In order to reliably obtain ΔTx of 60K or more in the range of 3,
The value of a indicating the composition ratio of Co is 0.042 ≦ a ≦ 0.29,
It is preferable that the value of b indicating the composition ratio of Ni be in the range of 0.042 ≦ b ≦ 0.43. In order to obtain good soft magnetic properties within the above range, the value of a indicating the composition ratio of Co is preferably in the range of 0.042 ≦ a ≦ 0.25. In order to obtain the value, it is more preferable that the value of b indicating the composition ratio of Ni is in the range of 0.042 ≦ b ≦ 0.1.

M is Zr, Nb, Ta, Hf, Mo, T
It is an element composed of one or more of i and V.
These are effective elements for forming amorphous, and are preferably in the range of 5 at% to 20 at%. Further, in order to obtain high magnetic properties, the content is more preferably set to 5 at% or more and 15 at% or less. Among these elements M, Zr is particularly effective. A part of Zr can be replaced by an element such as Nb. When the composition ratio c in the case of replacement is in the range of 0 ≦ c ≦ 0.6, a high ΔTx can be obtained. In particular, in order to make ΔTx 80 or more, the range of 0.2 ≦ c ≦ 0.4 is preferable.

B has a high amorphous forming ability, and is added in the range of 10 at% to 22 at% in the present invention. When B is less than 10 atomic%, ΔTx disappears,
It is not preferable because a high-density magnetic core main body 3 cannot be obtained. 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, C represented by T
r, W, Ru, Rh, Pd, Os, Ir, Pt, Al,
One or more elements of Si, Ge, C, and P 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. Outside of this range, the amorphous forming ability is undesirably deteriorated.

The soft magnetic metallic glass alloy of the above composition used in the present invention has magnetism at room temperature, and shows better magnetism by heat treatment. It should be noted that a suitable cooling rate is determined by the composition of the soft magnetic metallic glass alloy, the composition of the alloy, the means for production and the size, shape, etc. of the product.
A range of about ² to 10 ⁶ K / s can be used as a standard.

Next, if the raw material powder 16 having the above composition is prepared, it is put between the upper and lower punches 12 and 13 of the discharge plasma sintering apparatus shown in FIG. 2, and the inside of the chamber is evacuated. At the same time as applying pressure from above and below with the punches 12 and 13 and molding, for example, a pulse current as shown in FIG. In the spark plasma sintering process, the temperature of the raw material powder 16 can be quickly raised at a predetermined speed by the supplied current, and the temperature of the raw material powder 16 can be strictly controlled according to the value of the supplied current. The temperature can be controlled much more accurately than heating by sintering, and sintering can be performed under ideal conditions as designed in advance.

In the present invention, the sintering temperature depends on the raw material powder 1
It is necessary to set the temperature to 300 ° C. or higher in order to solidify and mold the material 6. However, the soft magnetic metallic glass alloy used as the raw material powder 16 has a large supercooled liquid temperature interval ΔT _x (T _x −
T _g ), pressure sintering in this temperature range makes it possible to preferably obtain a high-density magnetic core body 3. However, if the sintering temperature is close to the crystallization onset temperature, the formation of crystal nuclei (structural short-range order) and the start of crystal precipitation cause magnetic anisotropy, which may degrade soft magnetic properties. Further, the sintering temperature monitored by the mechanism of the spark plasma sintering apparatus is the temperature of the thermocouple 17 installed on the die 11, and is lower than the temperature applied to the raw material powder 16. Therefore, the sintering temperature in the present invention is preferably in the range of T ≦ Tx, where Tx is the crystallization start temperature and T is the sintering temperature.

In the present invention, the rate of temperature rise during sintering is preferably 10 ° C./min or more because a crystal phase is formed at a slow rate of temperature rise. Further, the pressure during sintering is preferably 3 t / cm ² or more, since if the pressure is too low, the magnetic core body cannot be formed.
Further, heat treatment may be performed on the obtained core body 3,
Thereby, magnetic characteristics can be improved. The heat treatment temperature at this time is not lower than the Curie temperature and not higher than the temperature at which crystals that deteriorate magnetic properties are precipitated, and specifically, is preferably in the range of 427 to 627 ° C., and more preferably 4 ° C.
77-527 ° C.

Since the magnetic core body 3 thus obtained has the same composition as the soft magnetic metallic glass alloy used as the raw material powder 16, it has excellent soft magnetic properties at room temperature, Shows better magnetism. For this reason, since the bulk magnetic core 1 composed of the magnetic core body 3 has excellent soft magnetic characteristics (soft magnetic characteristics), it can be widely applied to a magnetic core of a transformer, a magnetic core of a choke coil, and a magnetic core of a magnetic sensor. Can be
It is possible to obtain a magnetic core having excellent characteristics as compared with conventional materials.

In the above description, the method in which the raw material powder 16 made of a soft magnetic metallic glass alloy is formed by spark plasma sintering is used. However, the present invention is not limited to this. Thus, a bulk-shaped magnetic core body 3 can be obtained.

Further, the bulk magnetic core 1 of the present invention can also be obtained by providing a magnetic core body 3 obtained by pouring a molten metal of the above-mentioned soft magnetic metallic glass alloy into a predetermined mold and solidifying it by cooling. The melt of the soft magnetic metallic glass alloy is weighed using a single pure metal of Fe, Co, Ni, Zr and a pure boron crystal or the like as raw materials, respectively. , An arc furnace, a crucible furnace, a reverberatory furnace or the like. Next, the obtained molten alloy is poured into a mold having a predetermined shape, gradually cooled, and solidified, whereby a magnetic core body 3 having a desired shape is obtained. The magnetic core body 3 thus obtained has a high density and excellent soft magnetic characteristics, similarly to the magnetic core body obtained by sintering the alloy powder, so that the magnetic cores of transformers, choke coils, magnetic sensors, etc. Can be used as

The above-mentioned bulk magnetic core 1 has the following structure: ΔT _x = T _x −T _g
(Wherein T _x is the crystallization onset temperature, T _g represents the glass transition temperature.) Powder of a soft magnetic glassy alloy temperature interval [Delta] T _x of the supercooled liquid is 20K or more of the formula of the plasma sintered By sintering by the sintering method, it is possible to obtain a bulky magnetic core body 3 having a high density, so that core loss can be reduced. In the above-described bulk magnetic core 1, the sintering temperature is arbitrarily selected within a temperature range satisfying the relationship of T ≦ Tx where Tx is the crystallization start temperature and T is the sintering temperature. Since the magnetic core body 3 having the same composition as that of the soft magnetic metallic glass alloy having a high saturation magnetic flux density and excellent magnetic permeability can be obtained,
Core loss can be reduced. Furthermore, by performing a heat treatment on the magnetic core body 3 formed by sintering, a higher saturation magnetic flux density and an excellent magnetic permeability can be exhibited.

In the above-described bulk core 1, the core body 3 can be obtained not only by the plasma sintering method but also by the so-called casting method of cooling and solidifying the molten alloy, so that the manufacturing cost of the bulk core 1 can be reduced. Can be.

Further, the soft magnetic metallic glass alloy of the present invention comprises:
One or more elements of Fe, Co, and Ni as main components, and Zr, Nb, Ta, Hf, Mo, Ti, V
Containing one or more of the above elements and B and increasing the temperature interval ΔT _x of the supercooled liquid,
When sintering the alloy powder, the sintering temperature can be increased, and a higher-density core body 3 can be obtained, so that the core loss of the bulk core 1 can be reduced.

Further, the bulk magnetic core 1 of the present invention has ΔTx of 60 K or more, and has a composition represented by the following general formula, and has excellent magnetic permeability, small coercive force, and excellent soft magnetic properties. Since the magnetic core body 3 made of the soft magnetic metallic glass alloy is provided, the core loss can be reduced. _{(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 ≦ 20 atomic%, 10 atomic% ≦ y ≦ 22 atomic%, and M is an element composed of one or more of Zr, Nb, Ta, Hf, Mo, Ti, and V. _{Or, (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 at%, and M is Zr, Nb, Ta, H
f, Mo, Ti, an element composed of one or more of Ti and V, T is Cr, W, Ru, Rh, Pd, Os, I
It is an element composed of one or more of r, Pt, Al, Si, Ge, C, and P.

[0034]

【Example】

Example 1 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, the mother alloy was melted with a quartz nozzle, and the melt was heated to 40 m / S in an argon gas atmosphere.
The copper roll rotating at a pressure of 0.39 × 10 ⁵ Pa from the hole with a diameter of 0.4 mm at the lower end of the nozzle is blown out at a pressure of 0.39 × 10 ⁵ Pa to carry out a single roll method, whereby the width is 0.4 to 1 m.
m, a sample of a metallic glass alloy ribbon having a thickness of 13 to 22 μm was produced. The obtained sample was subjected to differential scanning calorimetry (DS
C).

FIG. 4 shows Fe ₆₀ Co ₃ Ni ₇ Zr ₁₀ B, respectively.
_{20, Fe 56 Co 7 Ni 7} Zr 10 B 20, Fe 49 Co 14 Ni 7
3 shows a DSC curve of a metallic glass alloy ribbon sample having a composition of Zr ₁₀ B ₂₀ and Fe ₄₆ Co ₁₇ Ni ₇ Zr ₁₀ B ₂₀ . In each of these samples, it was confirmed that a wide supercooled liquid region existed by increasing the temperature, and it was clarified that crystallization was caused by heating beyond the supercooled liquid region. . The temperature interval ΔTx in the supercooled liquid region is
ΔTx = Tx−Tg, where Tx−T shown in FIG.
The value of g exceeds 60K for any of the samples,
Is in the range. Substantial equilibrium, indicating a supercooled liquid region, was obtained over a wide range from 596 ° C (869K) to 632 ° C (905K), slightly below the temperature that indicates crystallization due to the exothermic peak.

FIG. 5 shows (Fe _{1 -ab} Co _a Ni _b ) ₇₀ Zr ₁₀
B is a triangular composition diagram showing the respective content dependence of Fe, Co and Ni to the value of ΔTx (= Tx-Tg) at ₂₀ having a composition system. As is clear from the results shown in FIG. 5, the value of ΔTx exceeds 25K in the entire range of the composition system of (Fe ₁ -ab Co _a Ni _b ) ₇₀ Zr ₁₀ B ₂₀ . Regarding the value of Tg, Co is changed from about 7 atomic% to 5%.
It was also clarified that increasing Tg in the range of about 0 atomic% monotonously increases Tg. On the other hand, as shown in FIG. 5, it was found that ΔTx had a large value in a composition system containing a large amount of Fe. To increase ΔTx to 60K or more, the Co content was set to 3 atomic% or more and 20 atomic% or less. , N
It is understood that the i content is preferably set to 3 atomic% or more and 30 atomic% or less. Note that (Fe _1-ab Co _a N
_ib ) In the composition formula of ₇₀ Zr ₁₀ B ₂₀ , the Co content is 3
(Fe _1-ab Co _a Ni _b ) should be 7
Since the atomic ratio is set to 0 atomic%, in order to set the Co composition ratio a to 0.042 or more and the Co content to 20 atomic% or less, the Co composition ratio a becomes 0.29 or less. Similarly, in order to increase the Ni content to 3 atomic% or more, the Ni composition ratio b is set to 0.042.
As described above, the composition ratio b of Ni becomes 0.43 or less in order to make the content 30 atomic% or less.

(Example 2) Fe, Co, Ni, Zr and N
b unitary pure metals and pure boron crystal were mixed arc melting in an Ar gas atmosphere _{Fe 56 Co 7 Ni 7 Zr 4} Nb 6
It was prepared master alloy B ₂₀ a composition. Next, this master alloy was melted in a quartz nozzle, and a single roll method was performed in which a molten alloy was blown out onto a rotating copper roll in an argon gas atmosphere to rapidly cool the sample. Manufactured. At this time, the nozzle diameter, the distance (gap) between the nozzle tip and the roll surface, the number of roll rotations,
By appropriately adjusting the injection pressure, the atmospheric pressure, and the like, an alloy ribbon having a thickness of 20 to 195 μm was obtained. Each sample was analyzed by X-ray diffraction. FIG. 6 shows the results. From FIG. 6, 2
It has a halo pattern at θ = 38-52 °, indicating that it has an amorphous single-phase structure.

Example 3 The atomic composition ratio was Fe ₅₆ Co ₇
A sample of a metallic glass alloy ribbon was produced in the same manner as in Example 1 except that Ni ₇ Zr _10-x Nb _x B ₂₀ (x = 0, 2, 4, 6, 8, _{10 at} %). . Next, the obtained sample is
The heat treatment was performed at a temperature of 527 ° C. (800 K) for 5 minutes. FIG. 7 shows the saturation magnetic flux density (Bs) of the manufactured sample,
The Nb content dependency of the coercive force (Hc), the magnetic permeability (μe) at 1 kHz, and the magnetostriction (λs) is shown. The saturation magnetic flux density (Bs) was N
As the amount of b was added, the concentration of the sample was decreased, and the sample containing no Nb was 0.1%.
9 (T) or more, about 0.75 for a sample containing 2 atomic% of Nb
(T). The values of the magnetic permeability (μe) were 5031 for the sample in a quenched state without Nb, 2228 for the sample containing 2 atomic% of Nb, and 10 atomic% for Nb.
In the sample containing, it decreased to 906. However, by performing the heat treatment, the magnetic permeability (μe) is remarkably improved, and a magnetic permeability (μe) of about 25000 can be obtained particularly in a sample containing 2 atomic% of Nb. Regarding the coercive force (Hc), in the sample in the quenched state, the sample containing no Nb and the sample containing 2 atomic% of Nb were both 50 A / m (=
0.625 Oe). In particular, the sample having Nb of 2 atomic% or less shows a very good value of 5 A / m (= 0.0625 Oe). When heat treatment is applied, Nb becomes 4
An excellent coercive force (Hc) can be obtained even in a sample containing at least atomic%. As described above, in order to obtain good soft magnetic properties, in this alloy sample, Nb
Is more preferably in the range of 0 to 2 atomic%. Therefore, it is possible to obtain a bulk magnetic core having a soft magnetic metallic glass alloy having a high saturation magnetic flux density, a low coercive force, and a high magnetic permeability. Is small,
It is possible to obtain a transformer having excellent power transmission efficiency.

Example 4 The atomic composition ratio was Fe ₅₆ Co ₇ N
except that the i ₇ Zr ₈ Nb ₂ B ₂₀ in the same manner as in Example 1 to obtain a thin strip of amorphous alloy. Next, the obtained ribbon was pulverized by pulverizing it in the air using a rotor mill. Among the obtained powders, those having a particle size of 53 to 105 μm were selected and used as raw material powders in the subsequent steps. About 2g
After filling the above raw material powder into a WC die using a hand press, the raw material powder was loaded into the die shown in FIG.
The inside of the chamber was pressurized with an upper and lower punch in an atmosphere of 3 × 10 ⁻⁵ torr, and the raw material powder was heated by applying a pulse wave to the raw material powder. As shown in FIG. 3, the pulse waveform was such that after 12 pulses had flowed, two pulses were paused, and the raw material powder was heated at a maximum current of 4700 to 4800A. The sintering was performed by heating the sample from room temperature to the sintering temperature while applying a pressure of 6.5 t / cm ² to the sample and holding the sample for about 5 minutes. Heating rate is 100 ° C
/ Min. From the obtained sintered body, a hollow cylindrical sample having an outer diameter of 10 mm, an inner diameter of 6 mm, and a thickness of 2 mm as shown in FIG. 1 was produced by wire electric discharge machining to obtain a magnetic core body. This core body was housed in a hollow annular core body storage case made of polyacetal resin as shown in FIG. At this time, epoxy resin was applied to two places on the bottom surface of the magnetic core main body storage case, and the magnetic core main body storage case and the magnetic core main body were fixed. In this way, three bulk cores subjected to the same treatment were obtained.

FIG. 8 shows the measurement results of the core loss of the bulk magnetic core of this embodiment. As a comparative example, a silicon steel plate (Si
FIG. 8 shows the relationship between the operating magnetic flux density and the core loss of the magnetic core obtained by laminating (3.5%). As is clear from FIG. 8, the cores of the present embodiment and the comparative example increase in core loss with an increase in operating magnetic flux density.
It can be seen that the core loss is always smaller within the range of the operating magnetic flux density measured than the magnetic core of the comparative example.

It should be noted that the present invention is not limited at all by the above-described examples, and it is needless to say that the composition, the manufacturing method, the heat treatment conditions, the shape, and the like can be variously modified.

[0042]

As described above, in the bulk magnetic core 1 of the present invention, ΔT _x = T _x −T _g (where T _x indicates a crystallization start temperature and T _g indicates a glass transition temperature). The soft magnetic metallic glass alloy powder having a temperature interval ΔT _x of the supercooled liquid represented by the following formula of 60 K or more is sintered by a plasma sintering method to form a bulk core body having a high density. Therefore, core loss can be reduced. In the bulk core of the present invention, the core body can be obtained not only by the plasma sintering method, but also by a so-called casting method of cooling and solidifying the molten alloy, so that the core loss is increased and the core loss is reduced. The manufacturing cost of the bulk core can be reduced.

Further, the soft magnetic metallic glass alloy of the present invention comprises:
One or more elements of Fe, Co, and Ni as main components, and Zr, Nb, Ta, Hf, Mo, Ti, V
One or two or more of the above elements and B, and the temperature interval ΔT _x of the supercooled liquid can be increased.
When sintering the alloy powder, the sintering temperature can be increased, and a higher-density core body can be obtained, so that the core loss of the bulk core can be reduced. Further, the bulk magnetic core of the present invention has ΔTx of 60K or more, and has a composition represented by the following general formula, and has excellent magnetic permeability, small coercive force, high saturation magnetic flux density, and soft magnetic properties. Since the magnetic core body made of a soft magnetic metallic glass alloy having excellent performance is provided, core loss can be reduced. (Fe _1-ab Co _a Ni _b ) _100-xy M _x B
_y, provided that 0.042 ≦ a ≦ 0.29 , 0.042 ≦ b ≦
0.43 , 5 atomic% ≦ x ≦ 20 atomic%, 10 atomic% ≦ y
≦ 22 atomic%, and M is Zr, Nb, Ta, Hf, M
It is an element composed of one or more of o, Ti, and V. Or (Fe _1-ab Co _a Ni _b ) _100-xyz M
_x B _y T _z where, 0.042 ≦ a ≦ 0.29,0.042 ≦ b ≦
0.43 , 5 atomic% ≦ x ≦ 20 atomic%, 10 atomic% ≦ y
≦ 22 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, and M is Z
an element composed of one or more of r, Nb, Ta, Hf, Mo, Ti, and V; T is Cr, W, Ru, R
h, Pd, Os, Ir, Pt, Al, Si, Ge, C,
P is an element composed of one or more of P.

[Brief description of the drawings]

FIG. 1 is an exploded view showing a bulk core according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a main structure of an example of a spark plasma sintering apparatus used for manufacturing a bulk magnetic core according to an embodiment of the present invention.

3 is a diagram showing an example of a pulse current waveform applied to a raw material powder in the discharge plasma sintering apparatus shown in FIG.

FIG. 4 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. 5 shows the relationship between the value of ΔTx (= Tx−Tg) and the value of Fe in a composition system of (Fe ₁ -ab Co _a Ni _b ) ₇₀ Zr ₁₀ B _20.
FIG. 4 is a triangular composition diagram showing the content dependence of Co, Ni and Co.

FIG. 6 is a diagram showing X-ray diffraction patterns at various plate thicknesses of a quenched ribbon having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₄ Nb ₆ B ₂₀ .

FIG. 7: 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. 8 is a view showing a core loss of a bulk core manufactured from a core body having a composition of Fe ₅₆ Co ₇ Ni ₇ Zr ₈ Nb ₂ B ₂₀ .

[Explanation of symbols]

1 Bulk core 2 Magnetic core storage case 3 Magnetic core body 4 Adhesive members

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihisa Inoue 35-29 Kawachi Moto Hasekura, Aoba-ku, Aoba-ku, Sendai City, Miyagi Prefecture −337839 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) H01F 1/12-1/38 H01F 27/24-27/26

Claims (4)

(57) [Claims] 1. One or two of Fe, Co, and Ni
With at least three or more elements as main components, Zr, Nb, Ta, Hf,
One or more elements of Mo, Ti, V and B
Wherein the temperature interval ΔTx of the supercooled liquid represented by the equation ΔTx = Tx−Tg (where Tx represents the crystallization start temperature and Tg represents the glass transition temperature) is 60 K or more , and
A bulk magnetic core comprising a magnetic core body obtained by sintering a soft magnetic metallic glass alloy powder represented by the following composition: (Fe _1-ab Co _a Ni _b ) _100-xy M _x B
_y, provided that 0.042 ≦ a ≦ 0.29, 0.042 ≦ b ≦
0.43, 5 at% ≦ x ≦ 20 at%, 10 at% ≦ y
≦ 22 atomic%, and M is Zr, Nb, Ta, Hf, M
Element consisting of one or more of o, Ti, and V
It is. 2. One or two of Fe, Co, and Ni.
With at least three or more elements as main components, Zr, Nb, Ta, Hf,
One or more elements of Mo, Ti, V and B
ΔTx = Tx−Tg (where Tx is the crystallization start
Temperature and Tg indicate the glass transition temperature).
The temperature interval ΔTx of the cooling liquid is 60K or more, and
The powder of the soft magnetic metallic glass alloy represented by the composition
Bulk magnetic body comprising a core body
heart. (Fe _1-ab Co _a Ni _b ) _100-xyz M
_x B _y T _z where, 0.042 ≦ a ≦ 0.29,0.042 ≦ b ≦
0.43, 5 at% ≦ x ≦ 20 at%, 10 at% ≦ y
≦ 22 atomic%, 0 atomic% ≦ z ≦ 5 atomic%, and M is Z
r, Nb, Ta, Hf, Mo, Ti, V
Or two or more elements, T is Cr, W, Ru, R
h, Pd, Os, Ir, Pt, Al, Si, Ge, C,
P is an element composed of one or more of P. 3. The bulk magnetic core according to claim 1 , wherein the powder of the Fe-based soft magnetic metallic glass alloy is heated at a rate of 10 ° C./min or more by a discharge plasma sintering method. A bulk magnetic core comprising a magnetic core body which is sintered by being heated. 4. A bulk magnetic core comprising a magnetic core body obtained by cooling and solidifying a molten metal of the soft magnetic metallic glass alloy according to claim 1 or 2 .