JP2000073148A - Iron base soft magnetic alloy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft magnetic alloy combining high saturation magnetic flux density and high permeability, furthermore low in magnetostriction and jointly having excellent frequency characteristics. SOLUTION: This alloy is the one expressed by the following compositional formula, and in which the crystal grains of Fe of a bcc structure with <=30 nm average crystal grain size are precipitated: (Fe1-aZa)xAyDzEv, where Z denotes either or both of Ni and Co, A denotes one or >=two kinds of elements among Zr, Nb and Hf, D denotes one or >=two kinds of elements among Ti, V, Cr and Mn, E denotes one or >=two kinds of elements among B, Al, Si, C, P, platinum group elements, Y, rare earth elements, Zn, Cd, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Se, Te, Li, Be, Mg, Ca, Sr and Ba, and 0<=a<=0.2, 75<=x<=93 atomic %, 4<=y<=9 atomic %, 0<z<=5 atomic % and 0.5<=v<=18 atomic % are satisfied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft magnetic alloy used for a magnetic device such as a magnetic head, a transformer and a choke coil, and more particularly to an Fe-based soft magnetic material having a high saturation magnetic flux density and excellent soft magnetic characteristics. It is about alloys.

[0002]

2. Description of the Related Art In general, the characteristics required for a soft magnetic alloy used for a magnetic head core, a magnetic core of a pulse motor, or a magnetic device such as a transformer or a choke coil are high saturation magnetic flux density and high magnetic permeability. A low coercive force, an appropriate magnetic anisotropy energy can be imparted, a squareness ratio (Ir / Is) can be controlled, and magnetostriction is small. Therefore, in the development of soft magnetic alloys, material research is being conducted on various alloy systems from these viewpoints. In particular, in a magnetic head, a soft magnetic alloy having a high saturation magnetic flux density is desired as a core material in order to cope with high coercivity of a magnetic recording medium accompanying an increase in recording density. For transformers and choke coils, in order to further reduce the size of electronic devices,
A soft magnetic alloy having a higher saturation magnetic flux density is desired. Conventionally, as the soft magnetic alloy, Fe-Si-A
Crystalline alloys such as l-based alloys (Sendust), Fe-Ni-based alloys (Permalloy) and silicon steel, and Fe-based and Co-based amorphous alloys are used.

[0003] However, although the Fe-Si-Al alloy has excellent soft magnetic properties, the saturation magnetic flux density is as low as about 1.1 T, and the Fe-Ni alloy has the saturation magnetic flux density in an alloy composition having excellent soft magnetic properties. Is as low as about 0.8 T, and silicon steel has a disadvantage that it has a high saturation magnetic flux density but is inferior to other soft magnetic properties. The Co-based amorphous alloy has excellent soft magnetic properties, but has a low saturation magnetic flux density of about 1.0 T, and the Fe-based amorphous alloy has a high saturation magnetic flux density of 1.5 T or more. Is obtained, but the soft magnetic properties are inferior. Furthermore, the thermal stability of these amorphous alloys is not sufficient, and there is a problem that has not been solved yet. As described above, the conventional soft magnetic alloy has a problem that it is difficult to combine high saturation magnetic flux density with excellent soft magnetic characteristics.

[0004] As a typical alloy developed in view of the above, there is Fe alloy in which a nanocrystalline phase is dispersed in an amorphous structure.
There is a -Zr-B alloy. This alloy is an excellent soft magnetic alloy having both high saturation magnetic flux density and high magnetic permeability, and having both high mechanical strength and high thermal stability. In particular, some compositions have a saturation magnetic flux density of 1.6 T or more.

[0005]

However, an Fe—Zr—B alloy having a composition having a saturation magnetic flux density exceeding 1.6 T has a large saturation magnetostriction constant λs of about 10 ⁻⁶ . On the other hand, the magnetic permeability μ is 20,000 to 3 at 1 kHz.
It is relatively low at about 000, and decreases to about 2,000 to 3,000 in a high frequency band of about 100 kHz. This is because F is increased to increase the saturation magnetic flux density.
Since the concentration of e is increased, it is difficult to rapidly cool the molten metal to obtain an amorphous phase, and as a result, the structure of the alloy obtained after the heat treatment becomes non-uniform and high magnetic permeability cannot be obtained. is there. As described above, the conventional Fe-Zr-B-based alloy has a problem that it is difficult to provide both high saturation magnetic flux density and high magnetic permeability.

The present invention has been made to solve the above problems, and provides a soft magnetic alloy having both high saturation magnetic flux density and high magnetic permeability, low magnetostriction and excellent frequency characteristics. The purpose is to:

[0007]

In order to achieve the above object, the present invention employs the following constitution. The Fe-based soft magnetic alloy of the present invention is obtained by quenching a melt of an alloy represented by the following composition formula to make the alloy amorphous, and then heat-treating the alloy to form a bcc-structure Fe crystal grain having an average grain size of 30 nm or less. It is characterized by being deposited. (Fe ₁ -aZ _a ) _x A _y D _z E _v where Z is one or both of Ni and Co, and A is one or two selected from the group consisting of Zr, Nb and Hf D is Ti, V, Cr, M
n is one or more elements selected from the group consisting of n, E is B, Al, Si, C, P, a platinum group element, Y,
Rare earth element, Zn, Cd, Ga, In, Ge, Sn, P
b, As, Sb, Bi, Se, Te, Li, Be, M
g, Ca, Sr and Ba are one or more elements selected from the group consisting of a, x, y,
z and v are 0 ≦ a ≦ 0.2, 75 atomic% ≦ x ≦ 93 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, 0 atomic% <z ≦ 5 atomic%, 0.5 atomic% ≦ v ≦ 18 atomic%. Further, it is preferable that B is always contained in the element E. Furthermore,
Preferably, the element D always contains Mn and V.

[0008] Fe and the element Z impart magnetism to the Fe-based soft magnetic alloy of the present invention. If the added amounts of Fe and the element Z are excessive, it is difficult to obtain an amorphous phase even by the liquid quenching method. And the magnetic permeability decreases. If the addition amounts of Fe and the element Z are small, the saturation magnetic flux density of the soft magnetic alloy decreases. Therefore, the composition ratio x, which is the total of Fe and the element Z, is set to 75 atomic% or more and 93 atomic% or less. Further, when a part of Fe is replaced with the element Z, the saturation magnetic flux density of the soft magnetic alloy,
It becomes possible to adjust permeability, magnetostriction, and the like. However,
For example, when Co is added as the element Z, since the magnetic permeability increases while the saturation magnetic flux density decreases, the composition ratio a of the element Z is set to 0.2 or less.

The element A is considered to be an element that reduces the rate of generation of fine crystal grain nuclei in the structure and facilitates the formation of an amorphous phase. It is effective for miniaturization. If the addition amount of the element A is small, the nucleus growth rate increases, the grain size of the crystal grains becomes coarse, and good soft magnetic characteristics cannot be obtained. On the other hand, if the amount of addition is excessive, the tendency of the formation of AB-based and Fe-A-based compounds after the heat treatment is increased, and the soft magnetic properties are reduced. Therefore, it is preferable that the composition ratio y of the element A is not less than 4 atomic% and not more than 9 atomic%.
It is preferably at least 8 atomic%. Of the element A,
In particular, since Zr and Nb have high amorphous forming ability, Zr and Nb
By adding at least one of the above, the addition amount of the element A can be reduced, and the addition amount of Fe can be relatively increased to further increase the saturation magnetic flux density of the soft magnetic alloy.

[0010] When the concentration of Fe is increased, the saturation magnetic flux density of the Fe-based soft magnetic alloy is increased, while the magnetic permeability is reduced. However, when the element D is added, the saturation magnetic flux density is improved without lowering the magnetic permeability. Becomes possible. The element D is mainly composed of a transition element. When the element D is added to the Fe-based soft magnetic alloy, a part of the element D is dissolved in Fe crystal grains having a bcc structure. When the element D forms a solid solution, the magnetic moment of the Fe phase decreases, but the Curie temperature rises, so that the saturation magnetic flux density of the Fe-based soft magnetic alloy at room temperature improves despite the decrease in the magnetic moment. Element D
Among them, Mn and V have a large effect of raising the Curie temperature, but in particular, adding V makes it possible to further raise the Curie temperature. Further, when both Mn and V are added simultaneously, the effect of increasing the saturation magnetic flux density without lowering the magnetic permeability of the Fe-based soft magnetic alloy is further increased.

However, when the element D is excessively added, Fe
Since the magnetic permeability of the base soft magnetic alloy decreases, the composition ratio z of the element D is set to 5 atomic% or less. Further, Mn and V as elements D
When the amount of Mn is excessive or small,
Since it is difficult to set the saturation magnetic flux density of the Fe-based soft magnetic alloy to 1.6 T or more, the composition ratio b of Mn in the element D is set to 1 atomic% to 3.25 atomic%. Further, in order to set the saturation magnetic flux density to 1.65 T or more, it is preferable that the range of the composition ratio b is set to 2 at% to 3 at%.

The element E enhances the ability to form an amorphous phase, remains at grain boundaries between fine crystal grains to be precipitated, prevents the crystal grains from becoming coarse, and has an adverse effect on soft magnetic properties during heat treatment.
Although it is considered that there is an effect of suppressing the formation of the -A-based compound phase, B is an element having the above-mentioned effect among elements E in particular. When the addition amount of the element E is small, the amorphous phase at the grain boundary becomes unstable, and a sufficient addition effect cannot be obtained. When the addition amount of the element E is excessive, the compound in the EA system and the Fe-E system cannot be obtained. The formation tendency is strong, and particularly when boride is formed, the heat treatment conditions for precipitating fine crystal grains are restricted, and good soft magnetic characteristics cannot be obtained. Therefore, element E
Is set at 0.5 atomic% or more and 18 atomic% or less. Further, in order to obtain a higher saturation magnetic flux density, it is preferable that the composition ratio v of the element E be 0.5 atomic% or more and 5 atomic% or less.

Further, the Fe-based soft magnetic alloy of the present invention has a 1k
It is preferable that the magnetic permeability in Hz is 5000 or more and the saturation magnetic flux density is 1.5 T or more. Furthermore, the Fe-based soft magnetic alloy of the present invention more preferably has a saturation magnetic flux density of 1.6 T or more.

[0014]

Embodiments of the present invention will be described below with reference to the drawings. The Fe-based soft magnetic alloy of the present invention is obtained by quenching a melt of an alloy represented by the following composition formula to be amorphous, and then heat-treating the alloy at a temperature equal to or higher than the crystallization temperature to obtain a bcc having an average crystal grain size of 30 nm or less. It is formed by precipitation of Fe crystal grains having a structure.

(Fe ₁ -aZ _a ) _x A _y D _z E _{v wherein} Z is one or both of Ni and Co, and A is one selected from the group consisting of Zr, Nb and Hf. Or two or more elements, where D is Ti, V, Cr, M
n is one or more elements selected from the group consisting of n, E is B, Al, Si, C, P, a platinum group element, Y,
Rare earth element, Zn, Cd, Ga, In, Ge, Sn, P
b, As, Sb, Bi, Se, Te, Li, Be, M
g, Ca, Sr and Ba are one or more elements selected from the group consisting of a, x, y,
z and v are 0 ≦ a ≦ 0.2, 75 atomic% ≦ x ≦ 93 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, 0 atomic% <z ≦ 5 atomic%, 0.5 atomic% ≦ v ≦ 18 atomic%.

The Fe-based soft magnetic alloy having this composition has a bcc structure (body-centered cubic structure) having an average crystal grain size of 30 nm or less.
And a crystalline phase mainly composed of fine crystal grains and an amorphous phase.

In the composition system of the present invention, the main component F
e and the element Z impart magnetism to the Fe-based soft magnetic alloy of the present invention, and are important for obtaining a high saturation magnetic flux density and excellent soft magnetic properties. When the composition ratio x indicating the total amount of Fe and the element Z exceeds 93% by weight, it is difficult to obtain an amorphous phase even by the liquid quenching method, and as a result, the structure of the alloy obtained after the heat treatment is not good. It is not preferable because it becomes uniform and high magnetic permeability cannot be obtained. On the other hand, when x is less than 75 atomic%, the saturation magnetic flux density decreases, and it becomes impossible to obtain a saturation magnetic flux density of 1.0 T or more, which is not preferable. Therefore, the range of x is set to 75 atomic% ≦ x ≦ 93 atomic%. Further, when a part of Fe is replaced with the element Z, the saturation magnetic flux density, magnetic permeability, magnetostriction, and the like of the Fe-based soft magnetic alloy can be adjusted. However, for example, when Co is added as the element Z, the magnetic permeability increases while the saturation magnetic flux density decreases. Therefore, the composition ratio a of the element Z is preferably 0.2 or less, more preferably 0.05 or less.

The element E has the effect of increasing the ability of the Fe-based soft magnetic alloy to form an amorphous phase, the effect of preventing the crystal structure from becoming coarse, and the effect of suppressing the formation of a compound phase that adversely affects magnetic properties in the heat treatment step. It is thought that there is
Is an element having the above-mentioned effect being large among the elements E.

Zr, Hf, and Nb are considered to hardly form a solid solution with α-Fe. However, by rapidly cooling the alloy to make it amorphous, Zr and Hf or Nb are dissolved in a supersaturated state. The heat treatment performed thereafter adjusts the solid solution amount of these elements to partially crystallize and precipitate as a fine crystal phase, thereby improving the soft magnetic properties of the obtained Fe-based soft magnetic alloy, It has the effect of reducing magnetostriction. Also,
In order to precipitate a fine crystal phase and to suppress the coarsening of the crystal grains of the fine crystal phase, it is considered necessary to leave an amorphous phase that may be an obstacle to crystal grain growth at the grain boundary. . Further, the grain boundary amorphous phase is formed by dissolving elements A such as Zr, Hf, and Nb discharged from α-Fe by increasing the heat treatment temperature, thereby deteriorating soft magnetic characteristics.
It is considered that the formation of a system compound is suppressed. Therefore, Fe-
Among Zr (Hf, Nb) alloys, B
Is important.

If v, which indicates the addition amount of the element E, is less than 0.5 atomic%, the amorphous phase at the grain boundary becomes unstable, so that a sufficient addition effect cannot be obtained. If v exceeds 18 atomic%, compounds tend to be formed in the EA system and the Fe-E system, and especially when boride is formed, heat treatment conditions for precipitating fine crystal grains are restricted. As a result, good soft magnetic characteristics cannot be obtained. By appropriately adding the element E in this manner, the average crystal grain size of the fine crystal phase to be precipitated can be adjusted to 30 nm or less.

Of the elements E, Al, Si, C, P and the like are generally used as amorphous forming elements, and the addition of these elements can be regarded as the same as the present invention. When Ru or another platinum group element is added, Fe
The effect of improving the corrosion resistance of the base soft magnetic alloy can also be obtained.
Also, Y, rare earth elements, Zn, Cd, Ga, In, G
e, Sn, Pb, As, Sb, Bi, Se, Te, L
When elements such as i, Be, Mg, Ca, Sr, and Ba are added, the magnetostriction can be adjusted.

In order to make it easier to obtain an amorphous phase,
It is preferable to include any of Zr, Hf, and Nb (element A), which have particularly high amorphous forming ability. Zr, Hf, N
Part of b can be replaced with another group 4A to 6A element. In addition, among Zr, Hf, and Nb, Hf is an extremely expensive element.
More preferably, it contains any one of b. Such an element A is a diffusion species that is relatively slow, and the addition of the element A is considered to have an effect of reducing the growth rate of fine crystal nuclei and an ability to form an amorphous phase, and is effective in making the structure finer.

If y indicating the amount of addition of the element A is less than 4 atomic%, the effect of reducing the nucleus growth rate is lost, and the crystal grain size becomes coarse, so that good soft magnetism cannot be obtained. In the case of an Fe-Hf-B alloy, the average crystal grain size at Hf = 5 atomic% is 13n.
In contrast, when Hf = 3 at%, the particle size becomes 39 nm and becomes coarse. If y, which indicates the amount of the element A added, exceeds 9 atomic%, the tendency of the formation of AB-based or Fe-A-based compounds increases, and good characteristics cannot be obtained. The band-shaped alloy becomes brittle, and it becomes difficult to process it into a predetermined shape.

Among them, Nb has a small absolute value of free energy of formation of an oxide, is thermally stable, and hardly forms an oxide. Therefore, when an Fe-based soft magnetic alloy is manufactured by adding these elements, the entire atmosphere during the manufacturing is not an inert gas atmosphere but an atmosphere in the air or a crucible used for rapidly cooling a molten metal. Since the nozzle can be manufactured in the atmosphere while supplying an inert gas to the tip of the nozzle, the manufacturing conditions are simplified and the Fe-based soft magnetic alloy can be manufactured at low cost.

When the concentration of Fe is increased, the saturation magnetic flux density of the Fe-based soft magnetic alloy is increased while the magnetic permeability is reduced. However, when the element D is added, the saturation magnetic flux density is improved without lowering the magnetic permeability. Becomes possible. The element D is mainly composed of a transition element. When the element D is added to the Fe-based soft magnetic alloy, a part of the element D is dissolved in Fe crystal grains having a bcc structure. When the element D forms a solid solution, the magnetic moment of the Fe phase decreases, but the Curie temperature rises, so that the saturation magnetic flux density of the Fe-based soft magnetic alloy at room temperature improves despite the decrease in the magnetic moment. Element D
Among them, Mn and V have a large effect of raising the Curie temperature, but in particular, adding V makes it possible to further raise the Curie temperature. Further, when both Mn and V are added simultaneously, the effect of increasing the saturation magnetic flux density without lowering the magnetic permeability of the Fe-based soft magnetic alloy is further increased.

However, if the element D is excessively added, Fe
Since the magnetic permeability of the base soft magnetic alloy decreases, the composition ratio z of the element D is set to 5 atomic% or less. Further, Mn and V as elements D
When the amount of Mn is excessive or small with respect to the amount of V, the saturation magnetic flux density of the Fe-based soft magnetic alloy is set to 1.
Since it is difficult to increase the temperature to 6 T or more, the composition ratio b of Mn is set to 1 to 3.25 at%. Further, in order to set the saturation magnetic flux density to 1.65 T or more, it is preferable that the range of the composition ratio b is set to 2 at% to 3 at%.

In addition, in the Fe-based soft magnetic alloy having the above composition, even if unavoidable impurities such as H, N, O, and S are contained to such an extent that desired characteristics are not deteriorated, the Fe-based soft magnetic alloy used in the present invention is used. Needless to say, it can be regarded as the same as the composition of the magnetic alloy.

According to the Fe-based soft magnetic alloy having the above composition,
Magnetic properties having a magnetic permeability at 1 kHz of 5000 or more and a saturation magnetic flux density of 1.5 T or more are obtained. In particular, depending on the composition, F with a saturation magnetic flux density of 1.6 T or more can be used.
An e-based soft magnetic alloy is obtained.

The Fe-based soft magnetic alloy of the present invention comprises a step of rapidly cooling an amorphous alloy or a crystalline alloy containing an amorphous phase having the above composition from a molten metal, Can usually be obtained by a heat treatment step for forming For the quenching of the molten metal, for example, means such as a so-called liquid quenching method of jetting the molten metal toward a rotating cooling roll to obtain an amorphous ribbon can be used. By performing heat treatment on the amorphous alloy in a predetermined temperature range, a part of the amorphous phase is crystallized, and a structure in which the amorphous phase and fine crystal grains having an average crystal grain size of 30 nm or less are mixed is formed. can get.

The reason why a fine crystal phase structure having an average crystal grain size of 30 nm or less was precipitated by the heat treatment is that a rapidly cooled amorphous alloy or the like is mainly composed of an amorphous material. This is because, at a certain temperature or higher, a fine crystal phase composed of crystal grains having a body-centered cubic structure (bcc structure) containing Fe as a main component and having an average crystal grain size of 30 nm or less is precipitated. The temperature at which the fine crystal phase of Fe having the body-centered cubic structure precipitates is about 480 to 550 ° C., depending on the composition of the alloy.
When the temperature is 525 ° C. or higher, the thermal stability of the Fe-based soft magnetic alloy is further improved. At a temperature higher than the temperature at which the fine crystal phase of Fe precipitates, a compound phase that deteriorates the soft magnetic properties such as Fe ₃ B or Fe ₃ Zr when Zr is contained in the alloy precipitates. The temperature at which such a compound phase precipitates is about 740 to 810 ° C., depending on the composition of the alloy.
Therefore, in the present invention, the holding temperature at the time of heat treatment of the amorphous alloy ribbon or the like is in the range of 480 ° C. to 810 ° C., and a fine crystal phase mainly composed of Fe having a body-centered cubic structure is preferably precipitated and It is preferably set according to the composition of the alloy so that the compound phase is not precipitated.

The rate of temperature rise when the temperature is raised to the above heat treatment temperature is preferably in the range of 20 to 200 ° C./min.
More preferably, the temperature is in the range of 200 ° C./min. If the heating rate is low, the production time will be long. Therefore, it is preferable that the heating rate is fast. However, the upper limit is about 200 ° C./min from the viewpoint of the performance of the heating device.

The time for keeping the amorphous alloy ribbon or the like at the above-mentioned holding temperature can be 0 to 60 minutes. Depending on the composition of the alloy, it is 0 minute, that is, the temperature is lowered immediately after the temperature rise and the holding time is reduced. Even without it, excellent soft magnetic characteristics can be obtained. Further, if the holding time is longer than 60 minutes, the soft magnetic properties are not improved, and the production time is prolonged and productivity is deteriorated, which is not preferable.

The above Fe-based soft magnetic alloy is represented by the following composition formula, in which Fe crystal grains having a bcc structure having an average crystal grain size of 30 nm or less are precipitated, and an element D which forms a solid solution in the Fe crystal grains is formed. Is added, the Curie temperature of the Fe-based soft magnetic alloy is increased, and the saturation magnetic flux density at room temperature is improved. Therefore, both the saturation magnetic flux density and the magnetic permeability of the Fe-based soft magnetic alloy can be increased. (Fe ₁ -aZ _a ) _x A _y D _z E _v where Z is one or both of Ni and Co, and A is one or two selected from the group consisting of Zr, Nb and Hf D is Ti, V, Cr, M
n is one or more elements selected from the group consisting of n, E is B, Al, Si, C, P, a platinum group element, Y,
Rare earth element, Zn, Cd, Ga, In, Ge, Sn, P
b, As, Sb, Bi, Se, Te, Li, Be, M
g, Ca, Sr and Ba are one or more elements selected from the group consisting of a, x, y,
z and v are 0 ≦ a ≦ 0.2, 75 atomic% ≦ x ≦ 93 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, 0 atomic% <z ≦ 5 atomic%, 0.5 atomic% ≦ v ≦ 18 atomic%.

According to the Fe-based soft magnetic alloy having the above composition,
It is possible to obtain magnetic properties having a magnetic permeability of 15000 or more at 1 kHz and a saturation magnetic flux density of 1.5T or more. In particular, an Fe-based soft magnetic alloy having a saturation magnetic flux density of 1.6 T or more can be obtained depending on the composition.

[0035]

EXAMPLE A predetermined amount of each of Fe, B, Zr, Mn, V, Ti, and Cr was weighed and mixed, and the mixture was melted using an arc melting furnace under a reduced-pressure Ar atmosphere to produce an ingot of the composition. . The ingot is put into a crucible, melted by high-frequency induction heating, melted is spouted onto a cooling roll (single roll) made of copper rotating under a reduced-pressure Ar atmosphere, and quenched to thereby rapidly cool the ribbon. I got The obtained quenched ribbon has a width of about 15 mm and a thickness of 20 to 30 μm.
m. By subjecting the obtained quenched ribbon to heat treatment under predetermined conditions to precipitate a fine crystalline phase, Fe
A base soft magnetic alloy ribbon was used. The magnetic properties of this Fe-based soft magnetic alloy ribbon were investigated. The results are shown in Tables 1, 2 and 3. The ripening conditions for the samples Nos. 1 to 17 shown in Table 1 were a temperature rising rate of 180 (° C./min), a heat treatment temperature (holding temperature) of 630 ° C., and a holding time of 5 minutes. The heat treatment conditions for the samples of Sample Nos. 18 to 30 shown in Tables 2 and 3 were the same as the samples of Table 1 except that the heat treatment temperatures were 560 ° C., 610 ° C., and 660 ° C.

The magnetic permeability (μ) was measured by punching a thin ribbon of an Fe-based soft magnetic alloy into a ring having an outer diameter of 10 mm and an inner diameter of 6 mm, laminating a plurality of them, winding them, and winding them. In Tables 1 to 3, numerical values in parentheses in the column of magnetic permeability indicate real values of magnetic permeability. Coercive force (Hc)
Was measured using a DC BH loop tracer, and the saturation magnetic flux density (Bs) was calculated from the magnetization measured at 10 kOe with a VSM. The saturation magnetostriction constant (λs) was measured by a three-terminal capacitance method.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

In Table 1, Fe ₉₄ Zr ₅ M of No. 16
The alloy ribbon having a composition of n _0.25 V _0.25 B _0.5 has a magnetic permeability (μ) of about 4,400 at 1 kHz, and
Does not reach 000. This is presumed to be due to the excessive amount of Fe of 94 atomic%. When the Zr content was 4 at% or less or the B content was 0.5 at% or less, the produced ribbon was embrittled and did not show good magnetic properties. Further, the alloy ribbon of composition No. 1 of Fe _85.5 Zr ₉ Mn _1.5 B ₃ and the alloy ribbon of composition 17 of Fe ₈₃ Zr ₆ Mn ₁ V ₁ B ₉ have a saturation magnetic flux density (Bs) and permeability. It shows that the magnetic susceptibility (μ) is slightly lower and the soft magnetic properties tend to deteriorate when Zr and B are excessive. Further, the alloy ribbon of the composition No. 9 having the composition of Fe _85.5 Zr ₆ Mn _3.5 V ₂ B ₃ has a total amount of Mn and V of 5.5 atomic%, and a high magnetic permeability (μ) is not obtained. You can see that. The other alloy ribbons have high saturation magnetic flux density and high magnetic permeability, and have excellent soft magnetic properties, because Mn and V are simultaneously and appropriately added in an appropriate amount. You can see that.

Next, Fe _86.5 Z of Sample Nos. 2 to 6 in Table 1 was used.
_{r 7 Mn x V 3.5-x} B 3 (x = 0,2.0,2.5,3.
The relationship between the magnetic properties and the composition ratios of Mn and V was investigated in detail for the alloy ribbon having the composition of 0,3.5). FIG.
Shows the measurement results of the crystallization start temperature of each alloy ribbon. The crystallization onset temperature was determined from the result of differential thermal analysis (DTA). The crystallization start temperature is in the range of 525 ° C. to 561 ° C. when the amount of Mn is in the range of 0 to 3.5% by weight, and is 525 ° C. when the amount of Mn is 2.5% by weight and the amount of V is 1.0% by weight. showed that. Therefore, by performing the heat treatment at a heat treatment temperature of 630 ° C., it is possible to sufficiently precipitate a fine crystalline phase from the amorphous phase. At this time, it is possible to control the volume fraction of the amorphous phase and the crystal by adjusting the heat treatment time.

FIG. 2 shows a quenched ribbon having a composition of Fe _86.5 Zr ₇ Mn _3.5 B ₃ and a heat treatment (600 ° C.,
The results of X-ray diffraction with the alloy ribbon obtained by holding for 1 hour) are shown. In the quenched ribbon, a halo diffraction pattern unique to amorphous is obtained. Further, in the alloy ribbon, a diffraction pattern due to the bcc-Fe phase was obtained, and it can be seen that a crystalline phase mainly composed of Fe was precipitated by the heat treatment. From this result, it can be seen that most of the structure of the present alloy ribbon has changed from amorphous to Fe phase (crystalline phase) having a bcc structure (body-centered cubic structure) by heat treatment. Further, the crystal phase of Fe having the bcc structure was found to be fine crystal grains having an average crystal grain size of about 10 to 30 nm based on the results obtained from the half width of the X-ray diffraction beak of the alloy ribbon.

FIG. 3 shows the real value of magnetic permeability at 100 kHz (| μ | (100 kHz)) and the dependence of the coercive force Hc on the amount of Mn. FIG. 4 shows the saturation magnetic flux density B
4 shows the Mn content dependence of s. It can be seen that the coercive force Hc decreases as the amount of Mn increases, and conversely, the magnetic permeability (| μ |) increases. When the amount of Mn is 2.5 atomic% or more, the magnetic permeability (| μ |) shows a high value exceeding 8,000, and reaches 10,000 when the amount of Mn is 3.5 atomic%. Further, the magnetic permeability changes almost linearly with the change in the amount of Mn, and it is estimated that desired characteristics can be easily obtained by changing the composition. But,
The behavior of the saturation magnetic flux density Bs shown in FIG. 4 is different from that of FIG. 3, and the saturation magnetic flux density Bs exceeds 1.62 T when the Mn content is in the range of 1 to 3.25 at%, and the Mn content is 2 to 2. In the range of 3 atomic%, the saturation magnetic flux density Bs is 1.6
The saturation magnetic flux density Bs reaches a maximum value of 1.69 T when the Mn content exceeds 7 T and the Mn content is around 2.5 at%. That is, Fe-Zr-
By simultaneously adding Mn and V to the base alloy composed of B, the saturation magnetic flux density Bs of the sample (sample numbers 20, 21, 24, 25, 29 to 38) to which only Mn or only V is added is larger than the saturation magnetic flux density Bs. Values have been obtained. Taking a common mode choke as an example of the application of the soft magnetic alloy, Bs ≧ 1.6T is desired as a characteristic of the soft magnetic alloy for the choke. According to the Fe-based soft magnetic alloy of the present invention,
As is clear from FIG. 4, even when the Mn content is 0 atomic%, it is 1.62.
T shows a high value, and when the amount of Mn is around 2.5 atomic%, 1.
It shows a very high value of 69T, which indicates that it has excellent characteristics as a soft magnetic alloy for chalk.

FIG. 5 shows the dependence of the saturation magnetostriction constant λs on the amount of Mn. As the amount of Mn increases, λs decreases,
It is almost 0 near the amount of 3.0 atomic%. From the above results, according to the Fe-based soft magnetic alloy of the present invention, Mn
1.67 T in the range of 2 to 3 atomic%
And a superior magnetic permeability (μ) exceeding 6,000 at the same time, and the magnetostriction can be reduced to almost zero.

Next, sample numbers 7, 8, 10 to 12 in Table 1 were used.
The _{Fe 86.5 Zr 6 Mn x V 4.5} -x B 3 (x = 0,1.5,
The relationship between the magnetic properties and the composition ratios of Mn and V was investigated in detail for alloy ribbons having compositions of 2.5, 3.5, and 4.5). FIG. 6 shows the measurement results of the crystallization start temperature of each alloy ribbon. The crystallization onset temperature was determined by differential thermal analysis (DTA) in the same manner as described above. The crystallization start temperature decreased as the Mn content increased, and was in the range of 490 ° C to 533 ° C when the Mn content was in the range of 0 to 4.5% by weight. Therefore, 63
By performing the heat treatment at a heat treatment temperature of 0 ° C., it is possible to sufficiently precipitate a fine crystalline phase from the amorphous phase.

Further, as a result of X-ray diffraction analysis of an alloy ribbon having a composition of Fe _86.5 Zr ₆ Mn _4.5 V _4.5-x B ₃ , bcc-Fe
A diffraction pattern based on the phases was obtained, and it was found that a crystalline phase mainly composed of Fe was precipitated by the heat treatment. Further, the crystal phase of Fe having the bcc structure was found to be fine crystal grains having an average crystal grain size of about 10 to 30 nm based on the results obtained from the half width of the X-ray diffraction beak of the alloy ribbon.

FIG. 7 shows the actual value of magnetic permeability at 100 kHz (| μ | (100 kHz)) and the dependence of the coercive force Hc on the amount of Mn. FIG. 8 shows the saturation magnetic flux density B
4 shows the Mn content dependence of s. As the amount of Mn increases, the coercive force Hc decreases, but becomes substantially constant in the range of 1.5 to 4.5 atomic%. Permeability (| μ |)
Increases as the amount of Mn increases, and the amount of Mn is 3.3 atomic%.
It shows the maximum value near. When the Mn content is 1.5 atomic% or more,
The magnetic permeability (| μ |) shows a high value exceeding 8,000,
Further, when the amount of Mn is 3.3 atomic%, it reaches 10,000. The saturation magnetic flux density Bs shown in FIG. 8 shows a maximum value of 1.72T when the amount of Mn is around 2.5 atomic%. Further, it can be seen that the saturation magnetic flux density Bs shows a high value of 1.65 T or more when the Mn content is in the range of 0 to 4.5 atomic%. That is, Mn is added to the base alloy composed of Fe-Zr-B.
And V at the same time, a sample to which only Mn or only V was added (sample numbers 20, 21, 24, 2
5, 29-38) are obtained.

FIG. 9 shows the dependence of the saturation magnetostriction constant λs on the amount of Mn. As the amount of Mn increases, λs decreases,
It is almost 0 near the amount of 4.5 atomic%. Mn
Even when the amount is about 2.5 atomic%, the saturation magnetostriction constant λs shows a low value of about 4.0 × 10 ⁻⁷ , which is a practically acceptable level. From the above results, according to the Fe-based soft magnetic alloy of the present invention, the high saturation magnetic flux density Bs exceeding 1.67 T in the case where the amount of Mn is in the range of 2 atomic% to 4.5 atomic%.
And an excellent magnetic permeability (μ) exceeding 8,500 at the same time, and the magnetostriction can be reduced to almost zero.

[0049]

As described in detail above, the Fe-based soft magnetic alloy of the present invention is represented by the following composition formula, in which bcc structure Fe grains having an average grain size of 30 nm or less are precipitated. The addition of the element D, which forms a solid solution in the Fe crystal grains, increases the Curie temperature of the Fe-based soft magnetic alloy and improves the saturation magnetic flux density at room temperature.
Both the saturation magnetic flux density and the magnetic permeability of the e-based soft magnetic alloy can be increased. (Fe ₁ -aZ _a ) _x A _y D _z E _v where Z is one or both of Ni and Co, and A is one or two selected from the group consisting of Zr, Nb and Hf D is Ti, V, Cr, M
n is one or more elements selected from the group consisting of n, E is B, Al, Si, C, P, a platinum group element, Y,
Rare earth element, Zn, Cd, Ga, In, Ge, Sn, P
b, As, Sb, Bi, Se, Te, Li, Be, M
g, Ca, Sr and Ba are one or more elements selected from the group consisting of a, x, y,
z and v are 0 ≦ a ≦ 0.2, 75 atomic% ≦ x ≦ 93 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, 0 atomic% <z ≦ 5 atomic%, 0.5 atomic% ≦ v ≦ 18 atomic%.

Further, since the element E always contains B, the ability to form an amorphous phase is enhanced, and the element E remains at the grain boundaries between the fine crystal grains to be precipitated and the crystal grains become coarse. Is prevented, and Fe-
By suppressing the generation of the A-based compound phase, a high magnetic permeability can be imparted to the Fe-based soft magnetic alloy. Further, since the element D always contains Mn and V, the saturation magnetic flux density can be further increased while maintaining high magnetic permeability.

According to the Fe-based soft magnetic alloy having the above composition,
It is possible to obtain magnetic properties having a magnetic permeability of 15000 or more at 1 kHz and a saturation magnetic flux density of 1.5T or more. In particular, an Fe-based soft magnetic alloy having a saturation magnetic flux density of 1.6 T or more can be obtained depending on the composition.

[Brief description of the drawings]

[1] _{Fe 86.5 Zr 7 Mn x V 3.5} -x B 3 (x = 0,
FIG. 4 is a diagram showing the Mn content dependence of the crystallization start temperature of an Fe-based soft magnetic alloy ribbon having a composition of 2.0, 2.5, 3.0, and 3.5).

FIG. 2 is a diagram showing the results of X-ray diffraction analysis of a quenched ribbon having a composition of Fe _86.5 Zr ₇ Mn _3.5 B ₃ and an Fe-based soft magnetic alloy ribbon.

[Figure 3] _{Fe 86.5 Zr 7 Mn x V 3.5} -x B 3 (x = 0,
2 shows the real value (| μ |) of the magnetic permeability and the Mn content dependency of the coercive force (Hc) of the Fe-based soft magnetic alloy ribbon having the composition of 2.0, 2.5, 3.0, 3.5). FIG.

[4] _{Fe 86.5 Zr 7 Mn x V 3.5} -x B 3 (x = 0,
FIG. 4 is a diagram showing the Mn content dependency of the saturation magnetic flux density (Bs) of an Fe-based soft magnetic alloy ribbon having a composition of 2.0, 2.5, 3.0, 3.5).

[5] _{Fe 86.5 Zr 7 Mn x V 3.5} -x B 3 (x = 0,
FIG. 4 is a diagram showing the Mn content dependence of the saturation magnetostriction constant (λs) of an Fe-based soft magnetic alloy ribbon having a composition of 2.0, 2.5, 3.0, 3.5).

[6] _{Fe 86.5 Zr 6 Mn x V 4.5} -x B 3 (x = 0,
FIG. 5 is a diagram showing the Mn content dependence of the crystallization start temperature of an Fe-based soft magnetic alloy ribbon having a composition of 1.5, 2.5, 3.5, 4.5).

7 _{Fe 86.5 Zr 6 Mn x V 4.5} -x B 3 (x = 0,
1.5 shows the real value (| μ |) of the magnetic permeability and the Mn content dependence of the coercive force (Hc) of the Fe-based soft magnetic alloy ribbon having the composition of 1.5, 2.5, 3.5, 4.5). FIG.

[8] _{Fe 86.5 Zr 6 Mn x V 4.5} -x B 3 (x = 0,
It is a figure which shows the Mn amount dependence of the saturation magnetic flux density (Bs) of the Fe-based soft magnetic alloy ribbon of the composition of 1.5, 2.5, 3.5, 4.5).

9 _{Fe 86.5 Zr 6 Mn x V 4.5} -x B 3 (x = 0,
FIG. 3 is a graph showing the Mn content dependence of the saturation magnetostriction constant (λs) of a Fe-based soft magnetic alloy ribbon having a composition of 1.5, 2.5, 3.5, 4.5).

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Makoto Nakazawa 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Teruo Bito 1-7 Yukitani Otsukacho, Ota-ku, Tokyo Alp (72) Inventor Akihiro Makino 1-7 Yukitani Otsuka-cho, Ota-ku, Tokyo Alps Electric Co., Ltd. (72) Inventor Akihisa Inoue 35 Kawachi Moto-Hasekura, Aoba-ku, Aoba-ku, Miyagi Prefecture Kawauchi Housing 11-806 (72) Inventor Takeshi Masumoto 3-8-22 Uesugi, Aoba-ku, Sendai, Miyagi Prefecture

Claims (7)

[Claims] An alloy having the following composition formula is quenched to be amorphous, and then heat-treated to precipitate bcc structure Fe grains having an average grain size of 30 nm or less. An Fe-based soft magnetic alloy characterized by the following. (Fe ₁ -aZ _a ) _x A _y D _z E _v where Z is one or both of Ni and Co, and A is one or two selected from the group consisting of Zr, Nb and Hf D is Ti, V, Cr, M
n is one or more elements selected from the group consisting of n, E is B, Al, Si, C, P, a platinum group element, Y,
Rare earth element, Zn, Cd, Ga, In, Ge, Sn, P
b, As, Sb, Bi, Se, Te, Li, Be, M
g, Ca, Sr and Ba are one or more elements selected from the group consisting of a, x, y,
z and v are 0 ≦ a ≦ 0.2, 75 atomic% ≦ x ≦ 93 atomic%, 4 atomic% ≦ y ≦ 9 atomic%, 0 atomic% <z ≦ 5 atomic%, 0.5 atomic% ≦ v ≦ 18 atomic%. 2. The Fe-based soft magnetic alloy according to claim 1, wherein the element E contains B. 3. The Fe-based soft magnetic alloy according to claim 1, wherein the element D contains Mn and V. 4. The composition ratio y and v in the composition formula are:
4. The Fe-based soft magnetic alloy according to claim 1, wherein 5 ≦ y ≦ 8 at% and 0.5 ≦ v ≦ 5 at%. 5. The composition ratio of Mn in the element D is b atomic%.
4. The Fe-based soft magnetic alloy according to claim 3, wherein, when the composition ratio of V is (z−b) atomic%, 1 atomic% ≦ b ≦ 3.25 atomic%. 6. The Fe-based soft magnetic alloy according to claim 1, wherein the magnetic permeability at 1 kHz is 5000 or more, and the saturation magnetic flux density is 1.5 T or more. 7. The Fe-based soft magnetic alloy according to claim 1, wherein the saturation magnetic flux density is 1.6 T or more.