JPH1171644A - Ferromagnetic metallic glass alloy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a ferromagnetic metallic glass alloy extremely wide in the temp. interval (δTx) in the supercoolant region, having excellent ferromagnetism at a room temp., capable of producing more thickly than the case of an amorphous alloy thin strip obtained by the conventional liquid rapid-quenching method and moreover excellent in material strength. SOLUTION: This alloy is composed in such a manner that a metallic glass alloy has a compsn. essentially consisting of Fe, and contains one or >= two kinds of elements selected from rare earth elements, one or >= two kinds of elements selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W and Cu, and B. The temp. interval δTx in the supercoolant region expressed by the equation of δTx=Tx-Tg (where Tx denotes the crystallization starting temp., and Tg denotes the glass transition temp.) is regulated to >=20 deg.K, and by subjecting to heat treatment at a temp. rising rate of >=20 deg.K/min, the alloy is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard magnetic metallic glass alloy, and more particularly to a hard magnetic metallic glass alloy which has excellent hard magnetism at room temperature and can be formed into a bulk permanent magnet molded body.

[0002]

2. Description of the Related Art Certain types of multi-element alloys have conventionally been
It has a large supercooled liquid region that is in the state of the supercooled liquid region before crystallization, and these are metallic glass alloys (glas
sy alloy). It is also known that this kind of metallic glass alloy becomes a bulk alloy much thicker than a thin ribbon of an amorphous alloy manufactured by a conventionally known liquid quenching method. By the way, conventionally, the thin ribbon of the amorphous alloy is 1960
Fe-PC-based amorphous alloy first produced in the 1970s, (Fe, C
o, Ni) -P-B based alloy, (Fe, Co, Ni) -Si-B based alloy, manufactured in the 1980's (Fe, Co, N)
i) -M (Zr, Hf, Nb) based alloy, (Fe, Co, N
i) -M (Zr, Hf, Nb) -B-based alloys are known, but all of these alloys need to be rapidly cooled at a cooling rate of 10 ⁵ K / s to be produced. The thickness of the object was 50 μm or less. In view of this, a thick bulk bonded magnet has been considered. This bonded magnet is composed of a magnetic powder produced by quenching a molten metal of an alloy mainly composed of Nd ₂ Fe ₁₄ B phase, and Fe ₃ B-Nd ₂ Fe. ₁₄ B
_It is made by compression molding or injection molding by mixing _1st exchange spring magnetic powder with rubber or plastic binder, so the magnetic properties are low due to the presence of the binder, and the material strength is weak. There was a problem. On the other hand, in the case of a metallic glass alloy, one having a thickness of several mm is obtained,
As such kind of metallic glass alloy, since 1988
Through 1991, Ln-Al-TM, Mg-Ln-T
M, Zr-Al-TM (where Ln is a rare earth element, TM
Represents a transition metal. ) Systems and other compositions 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 hard magnetic material, it is industrially difficult. There were big restrictions.
Therefore, conventionally, research and development of a metallic glass alloy which has a hard magnetism at room temperature and can obtain a thick bulk material has been promoted.

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 value of (Tx-Tg) is generally small, and in reality, it is poor in metallic glass forming ability and impractical. The presence of an alloy that has a temperature range of and can form metallic glass by cooling is
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.

[0005] The present invention has been made in view of the above circumstances, the temperature interval ΔTx of the supercooled liquid region is extremely wide,
An object of the present invention is to provide a hard magnetic metallic glass alloy which has excellent hard magnetism at room temperature, can be manufactured thicker than an amorphous alloy ribbon obtained by a conventional liquid quenching method, and has excellent material strength.

[0006]

The hard magnetic metallic glass alloy according to the present invention comprises Fe as a main component, one or more elements R selected from rare earth elements, and Ti, Z.
r, Hf, V, Nb, Ta, Cr, Mo, W, and Cu, containing one or more elements M and B, and ΔTx = Tx−Tg (where Tx is Starting temperature,
Tg indicates a glass transition temperature. ) Is characterized in that a metallic glass alloy having a temperature interval ΔTx of the supercooled liquid region represented by the formula of (2) of not less than 20K is heat-treated at a temperature increasing rate of not less than 20K / min.

Further, the hard magnetic metallic glass alloy according to the present invention may be characterized by being represented by the following composition formula. _{Fe 100-xyzw R x M y} T z B w where, T is one or two elements selected Co, from among Ni, x indicating the composition ratio, y, z, w in atomic% 2 atomic% ≦ x ≦ 15 atomic%, 2 atomic% ≦ y ≦ 20
Atomic%, 0 atomic% ≦ z ≦ 20 atomic%, 10 atomic% ≦ w ≦
30 atomic%.

Further, the hard magnetic metallic glass alloy according to the present invention may be characterized by being represented by the following composition formula. _{Fe 100-xyzwt R x M y} T z B w L t where, T is one or two elements selected Co, from among Ni, x indicating the composition ratio, y, z, w, t Is atomic%, 2 atomic% ≦ x ≦ 15 atomic%, 2 atomic% ≦ y ≦
20 atomic%, 0 atomic% ≦ z ≦ 20 atomic%, 10 atomic% ≦
w ≦ 30 atomic%, 0 atomic% ≦ t ≦ 5 atomic%, and the element L is Ru, Rh, Pd, Os, Ir, Pt, Al, S
1 selected from i, Ge, Ga, Sn, C, and P
A species or two or more elements.

In the present invention, the heat-treated metallic glass alloy includes a crystalline phase composed of one or two of an α-Fe phase and an Fe ₃ B phase and a crystalline phase composed of an Nd ₂ Fe ₁₄ B phase. It may be characterized by the fact that a quality phase is precipitated. In the present invention, inevitable impurities in production,
For example, even if a small amount of a rare earth oxide or the like is contained, it can be considered as being within the technical idea of the hard magnetic metallic glass alloy of the present invention.

[0010]

Embodiments of the present invention will be described below with reference to the drawings. The hard magnetic metallic glass alloy according to the present invention contains Fe as a main component, one or more elements R selected from rare earth elements, Ti, Zr,
One or more elements M selected from Hf, V, Nb, Ta, Cr, Mo, W, and Cu, and B,
ΔTx = Tx−Tg (where Tx is the crystallization start temperature, Tg
Indicates a glass transition temperature. ) Is obtained by heat-treating a metallic glass alloy having a temperature interval ΔTx of 20K or more in the supercooled liquid region represented by the formula (2), at a temperature increasing rate of 20 K / min or more. In the above composition system, when Cr is always contained, ΔTx is preferably 40K or more.

[0011] One of the hard magnetic glassy alloy according to the present invention, in the composition formula, can be represented by _{Fe 100-xyzw R x M y} T z B w, in this composition formula, T is Co,
Ni is one or two elements selected from Ni, and x, y, z, and w indicating the composition ratio are 2 atomic% ≦ x ≦ 1
5 atomic%, 2 atomic% ≦ y ≦ 20 atomic%, 0 atomic% ≦ z ≦
It is preferable that the condition of 20 at%, 10 at% ≦ w ≦ 30 at% is satisfied.

Next, another hard magnetic metallic glass composite according to the present invention will be described.
Gold is, in the composition formula, Fe_100-xyzwtR_xM_yT_zB_wL_t In this composition formula, T is Co or Ni.
One or two elements selected from the group consisting of
X, y, z, w, and t shown are 2 atomic% ≦ x ≦ 15 atoms
%, 2 atomic% ≦ y ≦ 20 atomic%, 0 atomic% ≦ z ≦ 20
%, 10 atomic% ≦ w ≦ 30 atomic%, 0 atomic% ≦ t ≦ 5
Atomic%, and the element L is composed of Ru, Rh, Pd,
Os, Ir, Pt, Al, Si, Ge, Ga, Sn,
One or more elements selected from C and P
is there. Further, the present invention relates to the above Fe_100-xyzwR_xM_yT_z
B_wOr the above formula Fe_100-xyzwtR_xM_yT_z
B_wL_tIn the composition formula, x indicating the composition ratio is atomic%.
And it is preferable that 2 atomic% ≦ x ≦ 12 atomic%.
It is more preferable that 2 atomic% ≦ x ≦ 8 atomic%.
Good. Further, the present invention relates to the above Fe_100-xyzwR_xM_y
T_zB_wOr the above formula Fe_100-xyzwtR_xM_y
T_zB_wL_tIn the composition formula, y representing the composition ratio is an atom
%, Preferably in the range of 2 atomic% ≦ y ≦ 15 atomic%.
More preferably, the range of 2 at% ≦ y ≦ 6 at% is more preferable.
preferable. Further, the present invention relates to the above Fe_100-xyzwR_xM_y
T_zB_wOr the above formula Fe _100-xyzwtR_xM_y
T_zB_wL_tIn the composition formula, z representing the composition ratio is an atom
% In the range of 0.1 atomic% ≦ z ≦ 20 atomic%
Is preferably in the range of 2 atomic% ≦ z ≦ 10 atomic%.
More preferred.

Further, the present invention relates to the above Fe _100-xyzw R _x
M _y T _z B _w a composition formula or the _{Fe 100-xyzwt} R _x
M _y T _z B _w L at _t a composition formula, element M (Cr _1-a
M ′ _a ), where M ′ is Ti, Zr, Hf, V, Nb,
It may be one or more elements selected from Ta, Mo, W, and Cu, wherein 0 ≦ a ≦ 1. Further, in the hard magnetic metallic glass alloy represented by such a composition formula, it is preferable that a indicating the composition ratio in the above composition formula is in the range of 0 ≦ a ≦ 0.5. In the present invention, the holding temperature during the heat treatment is 5
Heating at 00 to 850 ° C, preferably 550 to 750 ° C, is preferable in that a hard magnetic metallic glass alloy having improved coercive force and maximum magnetic energy product can be obtained. The hard magnetic metallic glass alloy after the heat treatment (after being heated) is cooled by, for example, water quenching.

Heating rate up to the holding temperature during the heat treatment
Is the coercive force and maximum magnetic energy of the hard magnetic metallic glass alloy.
20K / min or more from the viewpoint of improving
20 to 80 K / min, more preferably 40 K / min.
80 K / min. In the present invention, the above composition system
By performing the above-described heat treatment on the metallic glass alloy, α-
Fe phase and Fe_ThreeCrystalline phase consisting of one or two B phases
And Nd_TwoFe ₁₄To precipitate a crystalline phase consisting of phase B
Can be. This hard magnetic metallic glass alloy has an α-Fe phase
Soft magnetic phase with Nd_TwoFe₁₄B phase etc.
A mixed phase consisting of the hard magnetic phase where
The magnetic phase between the soft magnetic phase and the hard magnetic phase.
The combined exchange spring magnet characteristics are shown. What
Incidentally, in the present invention, even if the above-mentioned crystalline phase is precipitated
Is also referred to as a metallic glass alloy. Also, ΔTx
Amorpha with metallic glass and no ΔTx
Will be distinguished from

"Reason for limiting composition" In the composition system of the present invention,
Fe and Co as main components are elements that carry magnetism,
It is important to obtain high saturation magnetic flux density and excellent hard magnetic properties. In addition, ΔTx tends to increase in a component system containing a large amount of Fe, and setting the Co content to an appropriate value in a component system containing a large amount of Fe has an effect of increasing the value of ΔTx. The combined addition with other elements has the effect of increasing the value of ΔTx without deteriorating the magnetic properties, increasing the Curie point, and lowering the temperature coefficient. Specifically, in order to reliably obtain ΔTx, the value of z indicating the composition ratio of the element T is set in the range of 0 ≦ z ≦ 20,
In order to reliably obtain ΔTx of K or more, it is preferable that the value of z indicating the composition ratio of T be in the range of 2 atomic% ≦ z ≦ 10 atomic%. If necessary, part or all of Co may be replaced with Ni.

R is a rare earth metal (Y, La, Ce, P
r, Nd, Gd, Tb, Dy, Ho, Er). The R ₂ Fe ₁₄ B phase as these compounds is an element effective for generating uniaxial magnetic anisotropy and increasing the coercive force (iHc), and is in the range of 2 atomic% to 15 atomic%. And good. Further, in order to maintain a high magnetization without reducing the Fe content and maintain a magnetic balance with the coercive force (iHc), it is more preferable that the content be 2 atomic% or more and 12 atomic% or less. Preferably, 2 atomic% or more, 8 atomic%
The following range is recommended.

M is Ti, Zr, Hf, V, Nb, Ta,
One or two selected from Cr, Mo, W, and Cu
More than one kind of element. These are effective elements for forming an amorphous material, and are preferably in the range of 2 to 20 atomic%. Further, in order to obtain high magnetic properties, the content is more preferably 2 to 15 atomic%, and still more preferably 2 to 6 atomic%. Of these elements M, Cr is particularly effective. Cr
Represents a part of Ti, Zr, Hf, V, Nb, Ta, M
It can be replaced by one or more elements selected from o, W, and Cu. When the replacement ratio is in the range of 0 ≦ a ≦ 1, a high ΔTx can be obtained. Although it can be obtained, the range of 0 ≦ c ≦ 0.5 is preferable in order to reliably obtain a particularly high ΔTx. In addition, Cu of the element M has an effect of preventing the crystal from becoming coarse when crystallized to be hard magnetic, and has an effect of improving hard magnetic characteristics.

B has a high amorphous forming ability, and is added in the range of 10 at% to 30 at% in the present invention.
If the addition amount of B is less than 10 atomic%, ΔTx disappears, which is not preferable. If it is more than 30 atomic%, magnetic properties deteriorate, which is not preferable. In order to obtain higher amorphous forming ability and better magnetic properties, 14 atomic%
As described above, the content is more preferably set to 20 atomic% or less.

In the above composition system, R, represented by L,
u, Rh, Pd, Os, Ir, Pt, Al, Si, G
One, two or more elements selected from e, Ga, Sn, 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 hard magnetic properties deteriorate. Outside of this range, the glass forming ability is undesirably deteriorated.

In order to produce a hard magnetic metallic glass alloy material having the above composition system, for example, a powder of elemental element or a lump of elemental element (which may be partially alloyed in advance) of each component is prepared, and the above composition is prepared. These elemental powders or elemental agglomerates are mixed so as to be in the range, and then the mixed powder is melted in a crucible or other melting device in an inert gas atmosphere such as Ar gas to form a molten alloy having a predetermined composition. obtain. Next, the molten alloy is poured into a mold and gradually cooled, or quenched using a single roll method, whereby a hard magnetic metallic glass alloy material can be obtained. , A bulk permanent magnet molded article thicker than the amorphous alloy ribbon obtained by the method can be obtained. The rate of temperature rise during the heat treatment here is 20 K / min or more.
The single roll method is a method in which a molten metal is sprayed onto a rotating metal roll to rapidly cool the molten metal roll to obtain a ribbon-shaped amorphous alloy in which the molten metal is cooled. In the bulk hard magnetic metallic glass alloy thus obtained, an α-Fe phase or the like was precipitated particularly when the metallic glass alloy having the above composition was heat-treated at a heating rate of 20 K / min or more. Since a mixed phase composed of a soft magnetic phase and a hard magnetic phase on which Nd ₂ Fe ₁₄ B phase is precipitated is formed, and the exchange coupling characteristics between the soft magnetic phase and the hard magnetic phase can be improved, the coercive force and the maximum The magnetic energy product increases, and excellent hard magnetic properties are obtained. In addition, the bulk hard magnetic metallic glass alloy has an advantage that the magnetic properties are good and the material strength is high because a binder such as rubber or plastic is not interposed. It also has excellent corrosion resistance and good rust prevention.

[0021]

【Example】

(Production Example 1 of Metallic Glass Alloy) Fe, Co, and Nd
And a single pure metal of Cr or Zr 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 with a crucible, and 60 cmHg
In an argon gas atmosphere of 4000 r. p. 0.35 to 0.45 at the bottom of the crucible on the copper roll rotating at m
A sample of a metallic glass alloy thin ribbon having a width of 0.4 to 1 mm and a thickness of 20 to 30 μm was manufactured by performing a single roll method in which the material was blown out from a nozzle having a diameter of 0.5 mm at an injection pressure of 0.50 kgf / cm ² and rapidly cooled. . The surface of the single roll of the single roll liquid quenching device used here was finished with # 1500. The gap between the single roll and the tip of the nozzle was 0.30 mm. The obtained sample is analyzed by X-ray diffraction and differential scanning calorimetry (DSC), observed by a transmission electron microscope (TEM), and measured for magnetic properties at room temperature at 15 kOe by a vibrating sample magnetometer (VSM). did.

FIG. 1 shows Fe ₆₃ Co ₇ Nd _10-x Zr _x B
₂₀ shows the results of DSC curves obtained when samples having compositions of ₂₀ (x = 0, 2, 4, 6) were heated at a heating rate of 0.67 K / sec in the range of 127 to 827 ° C., respectively.
From FIG. 1, in the case of a metallic glass alloy ribbon sample having a composition of Fe ₆₃ Co ₇ Nd ₁₀ B ₂₀ , three or more exothermic peaks were observed, and it is considered that crystallization occurred in three or more stages. Glass transition temperature Tg below the onset temperature Tx
Is not observed, but when Zr is added and the amount added is increased, an endothermic reaction which is considered to correspond to Tg is observed at a temperature of Tx or lower when the amount of Zr added is 4 atomic% or more.

Next, Fe ₆₃ Co ₇ Nd _10-x Cr _x B ₂₀ (x
= 0,2,4,6) after vacuum-sealing a sample having the composition
560 ° C (833K) to 900 ° C using a muffle furnace
(1173K), FIG. 2 shows the results of examining the heat treatment temperature dependence of the magnetic properties when heat treatment was performed for a holding time of 300 seconds.

From the results shown in FIG. 2, regarding the saturation magnetization, the samples of the embodiment to which Cr was added (x = 2, 4, 6)
Is larger than that of the sample of the comparative example (x = 0) to which Cr is not added, and shows a high value of 1T or more. In any of the samples, the remanent magnetization shows a tendency to increase as the heat treatment temperature increases, and the samples (x = 2, 4, 6) of the examples to which Cr is added have Cr added. It can be seen that it is larger than that of the comparative sample (x = 0), rises to about 0.8 T, and shows a very high squareness ratio. Regarding the coercive force, the sample of the example in which Cr was added (x = 2, 4, 6) was different from the sample of the comparative example in which Cr was not added (x = 0) regardless of the amount of Cr added and the heat treatment temperature. It can be seen that the maximum energy products are larger for the samples with x = 4 and 6 although they are lower.

Next, after a metallic glass alloy ribbon sample having a composition of Fe ₆₃ Co ₇ Nd ₆ Cr ₄ B ₂₀ is vacuum-sealed, the rate of temperature rise during heat treatment using a muffle furnace is maintained at 10 K / min or more. Temperature 650 ° C (923K), retention time 300
FIG. 3 and Table 1 show the results of examining the temperature rise rate dependence of the magnetic characteristics in the case of seconds. Table 1 also shows the density of the rapidly quenched metallic glass alloy ribbon sample manufactured by the single roll method.

[0026]

[Table 1]

In Table 1, as-Q is an alloy ribbon sample in a quenched state without heat treatment, a is a heating rate during heat treatment,
∞ indicates the maximum value of the heating rate, Is indicates the saturation magnetization, Ir indicates the residual magnetization, Ir / Is indicates the squareness ratio, iHc indicates the coercive force, and (BH) max indicates the maximum magnetic energy product.

From the results shown in FIG. 3 and Table 1, Fe ₆₃ Co
_By setting the heating rate of the metallic glass alloy ribbon sample having a composition of ₇ Nd ₆ Cr ₄ B ₂₀ to 20 K / min or more, the saturation magnetization and the residual magnetization are not significantly changed. The magnetic force and the maximum magnetic energy product tend to increase. The coercive force at a heating rate of 40 K / min is about 400 kA / m, and the maximum magnetic energy product is 5
4 kJ / m ³ has been obtained, the coercive force at a heating rate 80K / minute to about 450kA / m, it is understood that the maximum magnetic energy product is 65 kJ / m ³ is obtained. Further, the coercive force and the maximum magnetic energy product are maximum when the heating rate is around 80 K / min.
Even if the speed is higher than 0 K / min, the magnetic properties are conversely reduced. Therefore, it is considered that the upper limit of the heating rate in the case of the metallic glass alloy of this composition is around 80 K / min.

FIG. 4 shows the IH loop before and after the heat treatment of the metallic glass alloy ribbon sample having the composition of Fe ₆₃ Co ₇ Nd ₆ Cr ₄ B ₂₀ . For comparison, Fe ₆₃ Co ₇ Nd ₁₀
Heat treatment before and after I-H loop for glassy alloy ribbon sample B ₂₀ a composition shown in FIG. As is clear from FIGS. 4 and 5, in the case of the amorphous alloy ribbon sample having the composition of Fe ₆₃ Co ₇ Nd ₁₀ B ₂₀ of the comparative example, the quenched state that has not been heat-treated shows soft magnetism. Shows hard magnetism by crystallization heat treatment. In addition, at the initial stage of crystal precipitation, the precipitated phase is very fine, and the coercive force decreases and the squareness deteriorates as the heat treatment temperature increases. It can be seen that grain growth occurs.
On the other hand, the Fe ₆₃ Co ₇ N
In the case of a metallic glass alloy ribbon sample having a composition of d ₆ Cr ₄ B _20, a quenched state that has not been heat-treated shows soft magnetism, and shows a hard magnetism by crystallization heat treatment. Further, it can be seen that the saturation magnetization and the residual magnetization are extremely high, the coercive force increases from the initial stage of crystal precipitation, and reaches a maximum after the first stage of crystallization, and then slightly decreases. This allows
It can be seen that the maximum energy product shows a larger value than the comparative example. This shows that the metallic glass alloy ribbon sample of the example is an exchange spring magnet composed of a soft magnetic phase and a hard magnetic phase.

(Production Example 2 of Metallic Glass Alloy) Fe and C
O, Nd, Cr simple pure metal and pure boron crystal are Ar
The mother alloy was manufactured by mixing and arc melting in a gas atmosphere. Next, the mother alloy was melted in a crucible, and a single roll method was performed in the same manner as in Production Example 2 described above.
Samples of metallic glass alloy ribbons having a width of 0.4 to 1 mm and a thickness of 20 to 30 μm were produced. The obtained sample was analyzed by X-ray diffraction and differential scanning calorimetry (DSC), observed with a transmission electron microscope (TEM), and then measured with a vibrating sample magnetometer (VS).
M), the magnetic properties were measured at room temperature and 15 kOe.

Next, the manufactured Fe₆₃Co₇Nd_10-xCr_xB
₂₀(X = 2, 4, 6 atomic%)
After vacuum-sealing the ribbon sample, 585 was filled using a muffle furnace.
° C (858K)-750 ° C (1023K), retention time 3
Dependence of magnetic properties on heat treatment temperature when heat treated for 00 seconds
Are shown in Table 2. For comparison, Fe ₆₃
Co₇Nd_TenB₂₀Metallic glass alloy ribbon sample of composition
After sealing in vacuum, 660 ° C. (933) using a muffle furnace.
K) ~ 750 ° C (1023K), heat for 300 seconds
Investigation of the dependence of magnetic properties on heat treatment temperature
The results are shown in Table 2. Table 2 shows the results of the single roll method.
Metallic glass alloy of each composition as-quenched
The density of the ribbon sample is also shown.

[0032]

[Table 2]

In Table 2, as-Q is an alloy ribbon sample that has not been heat-treated and remains in a quenched state, Ta is a heat treatment temperature, Is is a saturation magnetization, Ir is a residual magnetization, Ir / Is is a squareness ratio, and iHc is a preservation temperature. The magnetic force, (BH) max, indicates the maximum energy product.

From the results shown in Table 2, with respect to the saturation magnetization, the sample of the embodiment to which Cr was added was larger than the sample of the comparative example to which Cr was not added, and showed a high value of about 1 T or more. Recognize. Regarding the remanent magnetization, the sample of the example to which Cr was added was larger than the sample of the comparative example to which Cr was not added, and increased to about 0.6 to 0.9 T, showing a very high squareness ratio. You can see that it is.

Next, the temperature interval ΔTx in the supercooled liquid region was examined from the DSC curve when the samples of each composition shown in Table 2 were heated at a heating rate of 0.67 K / sec in the range of 127 to 827 ° C. However, in the comparative example, Fe ₆₃ Co ₇ Nd ₁₀ B ₂₀
ΔTx could not be observed in the amorphous alloy ribbon sample having the following composition, and in the metallic glass alloy ribbon sample having the composition Fe ₆₃ Co ₇ Nd ₈ Cr ₂ B ₂₀ , ΔTx = 51 K and Fe ₆₃ Co ₇ Nd
ΔT for a metallic glass alloy ribbon sample with a composition of ₆ Cr ₄ B ₂₀
For a metallic glass alloy ribbon sample having a composition of x = 40K and Fe ₆₃ Co ₇ Nd ₄ Cr ₆ B ₂₀ , ΔTx = 52K and Fe ₆₃ Co ₇ N
For a metallic glass alloy ribbon sample having a composition of d ₄ Zr ₆ B ₂₀ , Δ
Tx = 35 K, and it was found that the temperature interval ΔTx in the supercooled liquid region was wider when Cr was added.

[0036]

As described above, according to the present invention, one type or two or more types selected from rare earth elements containing Fe as a main component.
Or more elements R, Ti, Zr, Hf, V, Nb, T
a, a metallic glass alloy containing at least one element M selected from a, Cr, Mo, W, and Cu and B and having a temperature interval ΔTx of 20K or more in a supercooled liquid region is 20K /
By performing heat treatment at a temperature rising rate of more than one minute, the temperature interval ΔTx of the supercooled liquid region is wide, it can be manufactured thicker than the amorphous alloy ribbon obtained by the conventional liquid quenching method, and it shows excellent ferromagnetism at room temperature, Moreover, an amorphous hard magnetic metallic glass alloy having excellent material strength can be provided.

Further, the present _{invention, Fe 100-xyzw R x M} y
And those represented by T _z B _w a composition formula, T is Co, Ni
X, y, z, and w indicating the composition ratio are atomic%, and 2 atomic% ≦ x ≦
15 atomic%, 2 atomic% ≦ y ≦ 20 atomic%, 0 atomic% ≦ z
If the composition system is ≦ 20 atomic%, 10 atomic% ≦ w ≦ 30 atomic%, the temperature interval ΔTx of the supercooled liquid region is extremely wide, and it is manufactured thicker than the amorphous alloy ribbon obtained by the conventional liquid quenching method. Thus, an amorphous hard magnetic metallic glass alloy exhibiting excellent ferromagnetism at room temperature and having excellent material strength can be provided. Further, the present invention relates to Fe _100-xyzwt R _x M
_{y T z} B _w L _t becomes shall be represented by a composition formula, T is Co,
Ni is one or two elements selected from Ni, and x, y, z, w, and t indicating the composition ratio are atomic%, and 2 atomic% ≦ x ≦ 15 atomic% and 2 atomic% ≦ y ≦ 20 atomic%, 0
Atomic% ≦ z ≦ 20 atomic%, 10 atomic% ≦ w ≦ 30 atomic%, 0 atomic% ≦ t ≦ 5 atomic%, and the element L is Ru, R
h, Pd, Os, Ir, Pt, Al, Si, Ge, G
a, Sn, C, and P, if the composition system is one or more elements selected from the group consisting of Fe,
After there is _{100-xyzw R x M y T} z B w composed same effects of hard magnetic glassy alloy represented by the composition formula, by the element L is added, the hard magnetic metallic glass alloy corrosion resistance is excellent Can be provided.

In the present invention, since the above-mentioned heat treatment is performed on the metallic glass alloy having the above composition, α-Fe
Phase and a crystalline phase comprising one or two of Fe ₃ B phases;
A crystalline phase consisting of the Nd ₂ Fe ₁₄ B phase precipitates and α-Fe
Since a mixed phase consisting of a soft magnetic phase in which a phase is precipitated and a hard magnetic phase in which an Nd ₂ Fe ₁₄ B phase is precipitated is formed, the exchange coupling characteristic in which the soft magnetic phase and the hard magnetic phase are combined is improved. It will be shown.

[Brief description of the drawings]

FIG. 1 shows a rapidly cooled Fe _{63 Co 7} Nd _10-x Zr _x B ₂₀ (x = 0, 2, 4, 4) manufactured by a single roll method.
FIG. 6 is a view showing a result of obtaining a DSC curve of a ribbon sample having a composition of 6 atomic%).

FIG. 2 shows Fe ₆₃ Co ₇ Nd _10-x Cr _x B ₂₀ (x = 0,
2,4,6 atomic%) from 560 ° C to 9%.
FIG. 3 is a diagram showing the heat treatment temperature dependence of magnetic properties when heat treatment is performed at 00 ° C. for a holding time of 300 seconds.

FIG. 3 is a diagram showing the temperature rise rate dependence of magnetic properties when a ribbon sample having a composition of Fe ₆₃ Co ₇ Nd ₆ Cr ₄ B ₂₀ is heat-treated.

FIG. 4 is a diagram showing IH loops before and after heat treatment of a ribbon sample having a composition of Fe ₆₃ Co ₇ Nd ₆ Cr ₄ B ₂₀ .

FIG. 5 is a diagram showing IH loops before and after heat treatment of a ribbon sample having a composition of Fe ₆₃ Co ₇ Nd ₁₀ B ₂₀ .

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Akihiro Makino Alps Electric Co., Ltd., 1-7 Yukitani Otsuka-cho, Ota-ku, Tokyo (72) Inventor Akihisa Inoue 35 Kawamoto Moto Hasekura, Aoba-ku, Sendai, Miyagi Prefecture, Japan House 11-806

Claims (4)

[Claims] 1. A method according to claim 1, wherein one or more elements R containing Fe as a main component and selected from rare earth elements, Ti, Z
r, Hf, V, Nb, Ta, Cr, Mo, W, and Cu, containing one or more elements M and B, and ΔTx = Tx−Tg (where Tx is Starting temperature,
Tg indicates a glass transition temperature. A hard magnetic metallic glass alloy obtained by subjecting a metallic glass alloy having a temperature interval ΔTx of a supercooled liquid region represented by the following formula of 20 K or more to a heat treatment at a heating rate of 20 K / min or more. 2. The hard magnetic metallic glass alloy according to claim 1, wherein the alloy is represented by the following composition formula. _{Fe 100-xyzw R x M y} T z B w where, T is one or two elements selected Co, from among Ni, x indicating the composition ratio, y, z, w in atomic% 2 atomic% ≦ x ≦ 15 atomic%, 2 atomic% ≦ y ≦ 20
Atomic%, 0 atomic% ≦ z ≦ 20 atomic%, 10 atomic% ≦ w ≦
30 atomic%. 3. The hard magnetic metallic glass alloy according to claim 1, wherein the alloy is represented by the following composition formula. _{Fe 100-xyzwt R x M y} T z B w L t where, T is one or two elements selected Co, from among Ni, x indicating the composition ratio, y, z, w, t Is atomic%, 2 atomic% ≦ x ≦ 15 atomic%, 2 atomic% ≦ y ≦
20 atomic%, 0 atomic% ≦ z ≦ 20 atomic%, 10 atomic% ≦
w ≦ 30 atomic%, 0 atomic% ≦ t ≦ 5 atomic%, and the element L is Ru, Rh, Pd, Os, Ir, Pt, Al, S
1 selected from i, Ge, Ga, Sn, C, and P
A species or two or more elements. 4. The metallic glass alloy subjected to the heat treatment
Means that α-Fe phase and Fe _ThreeConsists of one or two phases B
Crystalline phase and Nd_TwoFe₁₄Crystalline phase consisting of phase B precipitates
The method according to any one of claims 1 to 3, wherein
Hard magnetic metallic glass alloy mentioned.