JP6604407B2 - Soft magnetic alloys and magnetic parts - Google Patents

Description

  The present invention relates to a soft magnetic alloy and a magnetic component.

  In recent years, low power consumption and high efficiency have been demanded in electronic / information / communication equipment and the like. Furthermore, the above demands are becoming stronger toward a low-carbon society. For this reason, reduction of energy loss and improvement of power supply efficiency are also required for power supply circuits of electronic, information, and communication devices. And the magnetic core of the magnetic element used for a power supply circuit is requested | required of the improvement of a saturation magnetic flux density, the reduction of a core loss (magnetic core loss), and the improvement of a magnetic permeability. If the core loss is reduced, the loss of power energy is reduced, and if the magnetic permeability is improved, the magnetic element can be reduced in size, so that high efficiency and energy saving can be achieved.

  Patent Document 1 describes a soft magnetic amorphous alloy of Fe-BM (M = Ti, Zr, Hf, V, Nb, Ta, Mo, W) system. This soft magnetic amorphous alloy has good soft magnetic properties such as a higher saturation magnetic flux density than commercially available Fe amorphous.

Japanese Patent No. 3342767

  As a method for reducing the core loss of the magnetic core, it is conceivable to reduce the coercive force of the magnetic body constituting the magnetic core.

  Patent Document 1 describes that the Fe-based soft magnetic alloy can improve soft magnetic properties by precipitating a fine crystalline phase. However, a composition that can stably precipitate a fine crystal phase has not been sufficiently studied.

  The present inventors have studied a composition that can stably precipitate a fine crystal phase. As a result, it has been found that a fine crystal phase can be stably precipitated even in a composition different from the composition described in Patent Document 1.

  An object of the present invention is to provide a soft magnetic alloy or the like that has a high saturation magnetic flux density and a low coercive force at the same time and further has improved surface properties.

In order to achieve the above object, a soft magnetic alloy according to the first aspect of the present invention provides:
Composition formula _{(Fe (1- (α + β} )) X1 α X2 β) a _{(1- (a + b + c} + d + e + f + g)) M a B b P c Si d C e S soft magnetic alloy consisting of f Ti _g consisting mainly composed,
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0.040 <c ≦ 0.15
0 ≦ d ≦ 0.060
0 ≦ e ≦ 0.030
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The initial microcrystal has a nanoheterostructure existing in an amorphous state.

In order to achieve the above object, the soft magnetic alloy according to the second aspect of the present invention provides:
Composition formula (Fe _{(1- (α + β))} X1 _α X2 _β ) _{(1- (a + b + c + d + e + f + g)) A} soft magnetic alloy composed of a main component consisting of M _a B _b P _c S i _d C _e S _f Ti _g
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0 <c ≦ 0.040
0 ≦ d ≦ 0.060
0.0005 <e <0.0050
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The initial microcrystal has a nanoheterostructure existing in an amorphous state.

  In the soft magnetic alloy according to the first and second aspects of the present invention, the initial crystallite may have an average particle size of 0.3 to 10 nm.

In order to achieve the above object, the soft magnetic alloy according to the third aspect of the present invention provides:
Composition formula (Fe _{(1- (α + β))} X1 _α X2 _β ) _{(1- (a + b + c + d + e + f + g)) A} soft magnetic alloy composed of a main component consisting of M _a B _b P _c S i _d C _e S _f Ti _g
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0.040 <c ≦ 0.15
0 ≦ d ≦ 0.060
0 ≦ e ≦ 0.030
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The soft magnetic alloy has a structure made of Fe-based nanocrystals.

In order to achieve the above object, a soft magnetic alloy according to the fourth aspect of the present invention provides:
Composition formula (Fe _{(1- (α + β))} X1 _α X2 _β ) _{(1- (a + b + c + d + e + f + g)) A} soft magnetic alloy composed of a main component consisting of M _a B _b P _c S i _d C _e S _f Ti _g
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0 <c ≦ 0.040
0 ≦ d ≦ 0.060
0.0005 <e <0.0050
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The soft magnetic alloy has a structure made of Fe-based nanocrystals.

  In the soft magnetic alloy according to the third and fourth aspects of the present invention, the Fe-based nanocrystal may have an average particle diameter of 5 to 30 nm.

  Since the soft magnetic alloy according to the first aspect of the present invention has the above-described characteristics, it becomes easy to obtain the soft magnetic alloy according to the third aspect of the present invention by heat treatment. Since the soft magnetic alloy according to the second aspect of the present invention has the above-described characteristics, it becomes easy to obtain the soft magnetic alloy according to the fourth aspect of the present invention by heat treatment. And the soft magnetic alloy which concerns on the said 3rd viewpoint, and the soft magnetic alloy which concerns on a 4th viewpoint become a soft magnetic alloy which has the high saturation magnetic flux density and the low coercive force simultaneously, and also improved the surface property.

  The following description regarding the soft magnetic alloy according to the present invention is common to the first to fourth aspects.

  The soft magnetic alloy according to the present invention may satisfy 0 ≦ α {1− (a + b + c + d + e + f + g)} ≦ 0.40.

  The soft magnetic alloy according to the present invention may have α = 0.

  The soft magnetic alloy according to the present invention may satisfy 0 ≦ β {1− (a + b + c + d + e + f + g)} ≦ 0.030.

  The soft magnetic alloy according to the present invention may have β = 0.

  The soft magnetic alloy according to the present invention may have α = β = 0.

  The soft magnetic alloy according to the present invention may have a ribbon shape.

  The soft magnetic alloy according to the present invention may be in powder form.

  The magnetic component according to the present invention is made of the soft magnetic alloy described above.

FIG. 1 is a schematic diagram of the single roll method. FIG. 2 is a schematic diagram of the single roll method.

  Hereinafter, first to fifth embodiments of the present invention will be described.

(First embodiment)
Soft magnetic alloy of the present embodiment, the composition formula _{(Fe (1- (α + β} )) X1 α X2 β) (1- (a + b + c + d + e + f + g)) M a B b P c Si d C e S f Ti g consisting mainly composed A soft magnetic alloy consisting of
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0.040 <c ≦ 0.15
0 ≦ d ≦ 0.060
0 ≦ e ≦ 0.030
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The initial microcrystal has a nanoheterostructure present in the amorphous.

  When heat-treating the soft magnetic alloy of the first embodiment, Fe-based nanocrystals are likely to precipitate. In other words, the soft magnetic alloy of the first embodiment is easy to use as a starting material for a soft magnetic alloy in which Fe-based nanocrystals are precipitated.

  When heat-treating the soft magnetic alloy (the soft magnetic alloy according to the first aspect of the present invention), Fe-based nanocrystals are likely to be precipitated in the soft magnetic alloy. In other words, the soft magnetic alloy is easy to use as a starting material for a soft magnetic alloy in which Fe-based nanocrystals are precipitated (the soft magnetic alloy according to the third aspect of the present invention). The initial microcrystals preferably have an average particle size of 0.3 to 10 nm.

  The soft magnetic alloy according to the third aspect of the present invention has the same main component as the soft magnetic alloy according to the first aspect and has a structure made of Fe-based nanocrystals.

  The Fe-based nanocrystal is a crystal having a particle size of nano-order and a Fe crystal structure of bcc (body-centered cubic lattice structure). In this embodiment, it is preferable to deposit Fe-based nanocrystals having an average particle size of 5 to 30 nm. A soft magnetic alloy in which such Fe-based nanocrystals are precipitated tends to have a high saturation magnetic flux density and a low coercive force.

  Hereinafter, each component of the soft magnetic alloy according to the present embodiment will be described in detail.

  M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V.

  The M content (a) satisfies 0.020 ≦ a ≦ 0.14. The M content (a) is preferably 0.040 ≦ a ≦ 0.10, and more preferably 0.050 ≦ a ≦ 0.080. When a is small, a crystal phase composed of crystals having a particle size larger than 30 nm is likely to be formed in the soft magnetic alloy before the heat treatment, and when the crystal phase is generated, Fe-based nanocrystals cannot be precipitated by the heat treatment. And a coercive force becomes high easily. When a is large, the saturation magnetic flux density tends to decrease.

  The B content (b) satisfies 0.020 <b ≦ 0.20. Moreover, 0.025 ≦ b ≦ 0.20 may be satisfied, 0.060 ≦ b ≦ 0.15 is preferable, and 0.080 ≦ b ≦ 0.12 is further preferable. When b is small, a crystal phase composed of crystals having a particle size larger than 30 nm tends to be formed in the soft magnetic alloy before the heat treatment, and when the crystal phase is generated, Fe-based nanocrystals cannot be precipitated by the heat treatment. And a coercive force becomes high easily. When b is large, the saturation magnetic flux density tends to decrease.

  The P content (c) satisfies 0.040 <c ≦ 0.15. Further, 0.041 ≦ c ≦ 0.15 may be satisfied, 0.045 ≦ c ≦ 0.10 is preferable, and 0.050 ≦ c ≦ 0.070 is further preferable. By containing P in the above range, particularly in a range where c> 0.040, the specific resistance of the soft magnetic alloy is improved and the coercive force is lowered. Furthermore, the surface properties of the soft magnetic alloy are improved. That is, when the soft magnetic alloy has a ribbon shape, the surface roughness becomes small. And the space factor of the core obtained from a soft magnetic alloy ribbon improves, and the saturation magnetic flux density of the said core improves. In addition, a core suitable for increasing current and size can be obtained. Further, when the soft magnetic alloy is in a powder form, the sphericity is improved. And the filling rate in the powder magnetic core obtained from soft-magnetic alloy powder improves. Furthermore, by improving both the specific resistance and the surface property, the magnetic permeability is improved, and a high magnetic permeability can be maintained even at higher frequencies. When c is small, the above effect is difficult to obtain. When c is large, the saturation magnetic flux density tends to decrease.

  The Si content (d) satisfies 0 ≦ d ≦ 0.060. That is, Si does not have to be contained. Further, 0.005 ≦ d ≦ 0.030 is preferable, and 0.010 ≦ d ≦ 0.020 is further preferable. By containing Si, the coercive force is particularly likely to be reduced. When d is large, the coercive force increases conversely.

  The content (e) of C satisfies 0 ≦ e ≦ 0.030. That is, C may not be contained. Further, 0.001 ≦ e ≦ 0.010 is preferable, and 0.001 ≦ e ≦ 0.005 is more preferable. By containing C, the coercive force is particularly likely to be reduced. If e is large, the coercive force will increase.

  The S content (f) satisfies 0 ≦ f ≦ 0.010. Moreover, it is preferable that it is 0.002 <= f <= 0.010. By containing S, it becomes easy to reduce coercive force and to improve surface properties. When f is large, the coercive force increases.

  The Ti content (g) satisfies 0 ≦ g ≦ 0.0010. Moreover, it is preferable that it is 0.0002 <= g <= 0.0010. By containing Ti, it becomes easy to reduce coercive force and to improve surface properties. When g is large, a crystal phase composed of crystals having a particle size larger than 30 nm is likely to be formed in the soft magnetic alloy before the heat treatment, and when the crystal phase is generated, Fe-based nanocrystals cannot be precipitated by the heat treatment. And a coercive force becomes high easily.

  In the soft magnetic alloy of this embodiment, it is particularly important to contain P and to contain S and / or Ti. When P is not contained, or when S and Ti are not contained, the surface property is particularly likely to deteriorate. Note that containing S indicates that f is not 0. More specifically, it indicates that f ≧ 0.001. To contain Ti means that g is not 0. More specifically, it indicates that g ≧ 0.0001.

  The Fe content (1- (a + b + c + d + e + f + g)) is not particularly limited, but is preferably 0.73 ≦ (1- (a + b + c + d + e + f + g)) ≦ 0.95. By setting (1− (a + b + c + d + e + f + g)) within the above range, a crystal phase composed of crystals having a grain size larger than 30 nm is more unlikely to occur when the soft magnetic alloy of the first embodiment is manufactured.

  Further, in the soft magnetic alloys of the first embodiment and the second embodiment, a part of Fe may be substituted with X1 and / or X2.

  X1 is at least one selected from the group consisting of Co and Ni. Regarding the content of X1, α = 0 may be used. That is, X1 may not be contained. Further, the number of atoms of X1 is preferably 40 at% or less, where the total number of atoms in the composition is 100 at%. That is, it is preferable to satisfy 0 ≦ α {1− (a + b + c + d + e + f + g)} ≦ 0.40.

  X2 is at least one selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements. With respect to the content of X2, β = 0 may be used. That is, X2 may not be contained. Further, the number of atoms of X2 is preferably 3.0 at% or less, where the number of atoms in the entire composition is 100 at%. That is, it is preferable to satisfy 0 ≦ β {1− (a + b + c + d + e + f + g)} ≦ 0.030.

  The range of substitution amount for substituting Fe with X1 and / or X2 is not more than half of Fe on an atomic basis. That is, 0 ≦ α + β ≦ 0.50. When α + β> 0.50, it is difficult to obtain the soft magnetic alloy of the second embodiment by heat treatment.

  Note that the soft magnetic alloys of the first embodiment and the second embodiment may contain elements other than the above as inevitable impurities. For example, it may be contained in an amount of 0.1% by weight or less with respect to 100% by weight of the soft magnetic alloy.

  Hereinafter, the manufacturing method of the soft magnetic alloy of 1st Embodiment is demonstrated.

  There is no limitation in particular in the manufacturing method of the soft-magnetic alloy of 1st Embodiment. For example, there is a method of producing a soft magnetic alloy ribbon by a single roll method. The ribbon may be a continuous ribbon.

  In the single roll method, first, pure metals of respective metal elements contained in the finally obtained soft magnetic alloy are prepared and weighed so as to have the same composition as the finally obtained soft magnetic alloy. And the pure metal of each metal element is melt | dissolved and mixed, and a mother alloy is produced. The method for dissolving the pure metal is not particularly limited. For example, there is a method in which the pure metal is melted by high-frequency heating after evacuation in a chamber. The master alloy and the finally obtained soft magnetic alloy usually have the same composition.

  Next, the produced mother alloy is heated and melted to obtain a molten metal (molten metal). Although there is no restriction | limiting in particular in the temperature of a molten metal, For example, it can be 1200-1500 degreeC.

  The schematic diagram of the apparatus used for the single roll method which concerns on this embodiment is shown in FIG. In the single roll method according to the present embodiment, the ribbon 24 is manufactured in the rotation direction of the roll 23 by injecting and supplying the molten metal 22 from the nozzle 21 to the roll 23 rotating in the direction of the arrow inside the chamber 25. Is done. In the present embodiment, the material of the roll 23 is not particularly limited. For example, a roll made of Cu is used.

  On the other hand, the schematic diagram of the apparatus used for the single roll method currently performed normally is shown in FIG. Inside the chamber 35, the molten metal 32 is sprayed from the nozzle 31 to the roll 33 rotating in the direction of the arrow to supply the ribbon 34 in the rotation direction of the roll 33.

  Conventionally, in the single roll method, it is considered that it is preferable to improve the cooling rate and quench the molten metal, and it is preferable to improve the cooling rate by increasing the contact time between the molten metal and the roll. It was thought. And, it was considered preferable to improve the cooling rate by widening the temperature difference between the molten metal and the roll. For this reason, it has been generally considered that the roll temperature is preferably about 5 to 30 ° C.

  As shown in FIG. 1, the present inventors further increase the time in which the roll 23 and the ribbon 24 are in contact with each other by rotating in the direction opposite to the normal roll rotation direction. Even if the temperature is raised to about 70 ° C., the ribbon 24 can be rapidly cooled. In the soft magnetic alloy having the composition of the first embodiment, the temperature of the roll 23 is made higher than before, and the time during which the roll 23 and the ribbon 24 are in contact with each other is further increased, so that the ribbon after cooling The uniformity of 24 is increased, and a crystal phase composed of crystals having a particle size larger than 30 nm is hardly generated. As a result, a soft magnetic alloy that does not include a crystal phase composed of crystals having a particle size larger than 30 nm can be obtained even in a composition in which a crystal phase composed of crystals larger than 30 nm is generated in the conventional method. As shown in FIG. 1, when the roll temperature is set to 5 to 30 ° C. as usual while rotating in the direction opposite to the normal roll rotation direction, the ribbon 24 is peeled off from the roll 23 immediately and rotated in the opposite direction. Was not obtained.

  In the single roll method, the thickness of the ribbon 24 obtained mainly by adjusting the rotation speed of the roll 23 can be adjusted. For example, the distance between the nozzle 21 and the roll 23, the temperature of the molten metal, etc. The thickness of the thin ribbon 24 obtained can be adjusted also by adjusting. Although there is no restriction | limiting in particular in the thickness of the thin strip 24, For example, it can be set as 15-30 micrometers.

  There is no particular limitation on the vapor pressure inside the chamber 25. For example, the vapor pressure inside the chamber 25 may be set to 11 hPa or less using Ar gas whose dew point has been adjusted. There is no particular lower limit for the vapor pressure inside the chamber 25. The vapor pressure may be reduced to 1 hPa or less by filling with Ar gas having a dew point adjusted, or the vapor pressure may be reduced to 1 hPa or less in a state close to vacuum.

  The ribbon 24, which is a soft magnetic alloy of the present embodiment, is an amorphous material that does not contain crystals having a particle size larger than 30 nm. And it has the nanoheterostructure which an initial stage microcrystal exists in an amorphous. When the soft magnetic alloy is subjected to the heat treatment described later, an Fe-based nanocrystalline alloy can be obtained.

  In addition, there is no restriction | limiting in particular in the method of confirming whether the ribbon 24 contains the crystal | crystallization with a particle size larger than 30 nm. For example, the presence or absence of crystals having a particle size larger than 30 nm can be confirmed by ordinary X-ray diffraction measurement.

In addition, the observation method of the presence or absence of the initial microcrystal and the average particle size is not particularly limited. For example, for a sample sliced by ion milling, using a transmission electron microscope, a limited field diffraction image, This can be confirmed by obtaining a nanobeam diffraction image, a bright field image, or a high resolution image. When using a limited-field diffraction image or a nanobeam diffraction image, a ring-shaped diffraction pattern is formed when the diffraction pattern is amorphous, whereas diffraction spots due to the crystal structure are formed when the diffraction pattern is not amorphous. It is formed. When a bright field image or a high resolution image is used, the presence or absence of initial microcrystals and the average grain size can be observed by visual observation at a magnification of 1.00 × 10 ^{5 to} 3.00 × 10 ⁵ times. .

  There is no restriction | limiting in particular in the temperature of a roll, a rotational speed, and the atmosphere inside a chamber. The roll temperature is preferably 4 to 30 ° C. for amorphization. The higher the rotation speed of the roll, the smaller the average grain size of the initial microcrystals tends to be 25-30 m / sec. Is preferable for obtaining initial microcrystals having an average particle size of 0.3 to 10 nm. The atmosphere inside the chamber is preferably in the air considering cost.

  Hereinafter, the ribbon 24 made of a soft magnetic alloy having a nano-heterostructure (the soft magnetic alloy according to the first aspect of the present invention) is subjected to heat treatment to produce a soft magnetic alloy having a Fe-based nanocrystal structure (the third magnetic material of the present invention). A method for producing a soft magnetic alloy) will be described.

  There are no particular restrictions on the heat treatment conditions for producing the soft magnetic alloy of this embodiment. Preferred heat treatment conditions vary depending on the composition of the soft magnetic alloy. Usually, a preferable heat treatment temperature is about 450 to 650 ° C., and a preferable heat treatment time is about 0.5 to 10 hours. However, depending on the composition, there may be a preferred heat treatment temperature and heat treatment time outside the above range. Moreover, there is no restriction | limiting in particular in the atmosphere at the time of heat processing. It may be performed under an active atmosphere such as in the air, or may be performed under an inert atmosphere such as in Ar gas.

  Moreover, there is no restriction | limiting in particular in the calculation method of the average particle diameter of Fe group nanocrystal contained in the soft magnetic alloy obtained by heat processing. For example, it can be calculated by observing using a transmission electron microscope. There is no particular limitation on the method for confirming that the crystal structure is bcc (body-centered cubic lattice structure). For example, it can be confirmed using X-ray diffraction measurement.

  And the ribbon which consists of a soft-magnetic alloy obtained by heat processing has high surface property. Here, when the surface property of the ribbon is high, the surface roughness of the ribbon is small. In the ribbon made of the soft magnetic alloy of this embodiment, the surface roughness Rv and the surface roughness Rz tend to be clearly smaller than those of the ribbon made of the conventional soft magnetic alloy. The surface roughness Rv is the maximum valley depth of the roughness curve, and the surface roughness Rz is the maximum height roughness. And the core obtained by winding the thin ribbon which consists of soft magnetic alloys with small surface roughness, or the core obtained by laminating | stacking has a high volume fraction of a magnetic body. Therefore, a good core (particularly a toroidal core) can be obtained.

  Further, as a method of obtaining the soft magnetic alloy of the present embodiment, there is a method of obtaining a soft magnetic alloy powder by, for example, a water atomizing method or a gas atomizing method other than the above-described single roll method. Hereinafter, the gas atomization method will be described.

  In the gas atomization method, a molten alloy at 1200 to 1500 ° C. is obtained in the same manner as the single roll method described above. Thereafter, the molten alloy is sprayed in a chamber to produce a powder.

  At this time, by setting the gas injection temperature to 50 to 200 ° C. and the vapor pressure in the chamber to 4 hPa or less, the preferable nanoheterostructure can be easily obtained.

  After producing a powder made of a soft magnetic alloy having a nano-heterostructure by gas atomization, heat treatment is performed at 400 to 600 ° C. for 0.5 to 10 minutes, so that each powder is sintered and the powder becomes coarse The Fe-based soft magnetic alloy having an average particle size of 10 to 50 nm can be obtained by accelerating the diffusion of elements while preventing them from being reached, allowing a thermodynamic equilibrium state to be reached in a short time, removing strain and stress, and the like. It becomes easy to obtain.

  The powder made of the soft magnetic alloy of the first embodiment and the second embodiment described later has excellent surface properties and high sphericity. And the filling rate of the powder magnetic core obtained from the powder which consists of soft magnetic alloys with high sphericity improves.

(Second Embodiment)
Hereinafter, a second embodiment of the present invention will be described. Description of the same parts as those in the first embodiment is omitted.

  In the second embodiment, the soft magnetic alloy before the heat treatment is made of only amorphous. Even if the soft magnetic alloy before the heat treatment is made of only amorphous, does not contain the initial microcrystal, and does not have the nanoheterostructure, the soft magnetic alloy having the Fe-based nanocrystal structure by performing the heat treatment, that is, The soft magnetic alloy according to the third aspect of the present invention can be obtained.

  However, compared to the first embodiment, it is difficult to precipitate Fe-based nanocrystals by heat treatment, and it is difficult to control the average particle size of Fe-based nanocrystals. Therefore, it is difficult to obtain excellent characteristics as compared with the first embodiment.

(Third embodiment)
Hereinafter, a third embodiment of the present invention will be described. Description of the same parts as those in the first embodiment is omitted.

Soft magnetic alloy according to the present embodiment, the composition formula _{(Fe (1- (α + β} )) X1 α X2 β) (1- (a + b + c + d + e + f + g)) consisting of _{M a B b P c Si d} C e S f Ti g Main A soft magnetic alloy comprising components,
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0 <c ≦ 0.040
0 ≦ d ≦ 0.060
0.0005 <e <0.0050
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
The initial microcrystals have a nanoheterostructure present in the amorphous.

  When heat-treating the soft magnetic alloy (the soft magnetic alloy according to the second aspect of the present invention), Fe-based nanocrystals are likely to be precipitated in the soft magnetic alloy. In other words, the soft magnetic alloy described above is easy to use as a starting material for a soft magnetic alloy in which Fe-based nanocrystals are precipitated (the soft magnetic alloy according to the fourth aspect of the present invention). The initial microcrystals preferably have an average particle size of 0.3 to 10 nm.

  The soft magnetic alloy according to the fourth aspect of the present invention has the same main component as the soft magnetic alloy according to the second aspect and has a structure made of Fe-based nanocrystals.

  The content (c) of P satisfies 0 <c ≦ 0.040. Further, 0.010 ≦ c ≦ 0.040 is preferable, and 0.020 ≦ c ≦ 0.030 is more preferable. By containing P within the above range, the coercive force of the soft magnetic alloy is lowered. When c = 0, the above effect cannot be obtained.

  The C content (e) satisfies 0.0005 <e <0.0050. Further, 0.0006 ≦ e ≦ 0.0045 is preferable, and 0.0020 ≦ e ≦ 0.0045 is more preferable. By making e larger than 0.0005, the coercive force of the soft magnetic alloy is particularly likely to be lowered. When e is too large, the saturation magnetic flux density and surface properties are lowered.

(Fourth embodiment)
The fourth embodiment of the present invention will be described below. The description of the same parts as those in the third embodiment is omitted.

  In the fourth embodiment, the soft magnetic alloy before the heat treatment is made of only amorphous. Even if the soft magnetic alloy before the heat treatment is made of only amorphous, does not contain the initial microcrystal, and does not have the nanoheterostructure, the soft magnetic alloy having the Fe-based nanocrystal structure by performing the heat treatment, that is, The soft magnetic alloy according to the fourth aspect of the present invention can be obtained.

  However, compared to the third embodiment, Fe-based nanocrystals are hardly precipitated by heat treatment, and it is difficult to control the average particle size of the Fe-based nanocrystals. Therefore, it is difficult to obtain excellent characteristics as compared with the third embodiment.

(Fifth embodiment)
The magnetic component according to the fifth embodiment, in particular, the magnetic core and the inductor are obtained from the soft magnetic alloy according to any one of the first to fourth embodiments. Hereinafter, although the method of obtaining the magnetic core and inductor which concerns on 5th Embodiment is demonstrated, the method of obtaining a magnetic core and an inductor from a soft magnetic alloy is not limited to the following method. In addition to inductors, applications of magnetic cores include transformers and motors.

  Examples of a method for obtaining a magnetic core from a ribbon-shaped soft magnetic alloy include a method of winding and laminating a ribbon-shaped soft magnetic alloy. When laminating thin ribbon-shaped soft magnetic alloys via an insulator, a magnetic core with further improved characteristics can be obtained.

  Examples of a method for obtaining a magnetic core from a powder-shaped soft magnetic alloy include a method in which a magnetic core is appropriately mixed with a binder and then molded using a mold. In addition, by applying an oxidation treatment, an insulating film or the like to the powder surface before mixing with the binder, the specific resistance is improved and the magnetic core is adapted to a higher frequency band.

  There is no restriction | limiting in particular in a shaping | molding method, Molding using a metal mold | die, mold shaping | molding, etc. are illustrated. There is no restriction | limiting in particular in the kind of binder, A silicone resin is illustrated. There is no particular limitation on the mixing ratio of the soft magnetic alloy powder and the binder. For example, a binder of 1 to 10% by mass is mixed with 100% by mass of the soft magnetic alloy powder.

For example, a space factor (powder filling rate) is 70% or more and 1.6% by mixing a binder of 1 to 5% by mass with 100% by mass of the soft magnetic alloy powder and compression molding using a mold. A magnetic core having a magnetic flux density of 0.45 T or more and a specific resistance of 1 Ω · cm or more when a magnetic field of × 10 ⁴ A / m is applied can be obtained. The above characteristics are equivalent to or better than general ferrite cores.

Further, for example, by mixing 1 to 3% by weight of a binder with respect to 100% by weight of the soft magnetic alloy powder and compressing with a mold under a temperature condition equal to or higher than the softening point of the binder, the space factor is 80%. As described above, a dust core having a magnetic flux density of 0.9 T or more and a specific resistance of 0.1 Ω · cm or more when a magnetic field of 1.6 × 10 ⁴ A / m is applied can be obtained. The above characteristics are superior to general dust cores.

  Furthermore, the core loss is further reduced and the usefulness is increased by heat-treating the formed body having the above-described magnetic core after the forming as a strain removing heat treatment. Note that the core loss of the magnetic core is reduced by reducing the coercive force of the magnetic body constituting the magnetic core.

  An inductance component can be obtained by winding the magnetic core. There are no particular restrictions on the manner in which the winding is applied and the method of manufacturing the inductance component. For example, a method of winding a winding at least one turn or more around the magnetic core manufactured by the above method can be mentioned.

  Further, when soft magnetic alloy particles are used, there is a method of manufacturing an inductance component by press-molding and integrating the winding coil in a state where the winding coil is built in the magnetic body. In this case, it is easy to obtain an inductance component corresponding to a high frequency and a large current.

  Further, when soft magnetic alloy particles are used, a soft magnetic alloy paste obtained by adding a binder and a solvent to the soft magnetic alloy particles and a paste obtained by adding a binder and a solvent to the conductor metal for the coil. An inductance component can be obtained by heating and firing after alternately laminating and laminating the conductive paste. Alternatively, by producing a soft magnetic alloy sheet using a soft magnetic alloy paste, printing a conductor paste on the surface of the soft magnetic alloy sheet, laminating and firing these, an inductance component in which the coil is built in the magnetic body is obtained. Obtainable.

  Here, when producing an inductance component using soft magnetic alloy particles, it is excellent to use a soft magnetic alloy powder having a maximum particle size of 45 μm or less and a center particle size (D50) of 30 μm or less. It is preferable for obtaining the Q characteristic. In order to set the maximum particle size to 45 μm or less in terms of sieve diameter, a sieve having an opening of 45 μm may be used, and only the soft magnetic alloy powder passing through the sieve may be used.

  The Q value in the high frequency region tends to decrease as the soft magnetic alloy powder having a large maximum particle size is used. Particularly when the soft magnetic alloy powder having a maximum particle size exceeding 45 μm in the sieve diameter is used, The Q value may be greatly reduced. However, if the Q value in the high frequency region is not important, soft magnetic alloy powder having a large variation can be used. Since soft magnetic alloy powders with large variations can be manufactured at a relatively low cost, it is possible to reduce costs when using soft magnetic alloy powders with large variations.

  As mentioned above, although each embodiment of this invention was described, this invention is not limited to said embodiment.

  There is no particular limitation on the shape of the soft magnetic alloy. As described above, a thin film shape and a powder shape are exemplified, but other than that, a block shape and the like are also conceivable.

  There is no restriction | limiting in particular in the use of the soft magnetic alloy (Fe-based nanocrystal alloy) of 1st Embodiment-4th Embodiment. For example, magnetic parts are mentioned, and among these, a magnetic core is particularly mentioned. It can be suitably used as a magnetic core for an inductor, particularly a power inductor. The soft magnetic alloy according to this embodiment can be suitably used for a thin film inductor and a magnetic head in addition to a magnetic core.

  Hereinafter, the present invention will be specifically described based on examples.

(Experimental example 1)
The raw metal was weighed so as to have the alloy compositions of the examples and comparative examples shown in the following table, and was melted by high-frequency heating to prepare a master alloy. The compositions of sample numbers 13 and 14 are generally well-known amorphous alloy compositions.

  Thereafter, the produced master alloy was heated and melted to form a metal in a molten state at 1250 ° C., and then the roll was rotated at a rotational speed of 25 m / sec. The metal was sprayed onto a roll by a single roll method that was rotated at a thin film to create a ribbon. The material of the roll was Cu.

  The roll was rotated in the direction shown in FIG. Also, by setting the differential pressure between the chamber and the injection nozzle to 105 kPa, the nozzle diameter 5 mm slit, the flow rate 50 g, and the roll diameter φ300 mm, the thickness of the obtained ribbon is 20-30 μm and the width of the ribbon is 4 mm. -5 mm, and the length of the ribbon was set to several tens of meters.

  X-ray diffraction measurement was performed on each obtained ribbon to confirm the presence or absence of crystals having a particle size larger than 30 nm. When there is no crystal having a particle size larger than 30 nm, it is assumed to be composed of an amorphous phase, and when a crystal having a particle size larger than 30 nm is present, it is composed of a crystalline phase. In all examples except for sample number 322, which will be described later, the initial microcrystals had a nanoheterostructure existing in an amorphous state.

  Thereafter, heat treatment was performed on the ribbons of Examples and Comparative Examples under the conditions shown in the table below. Saturation magnetic flux density, coercive force and surface roughness (Rv and Rz) were measured for each ribbon after the heat treatment. The saturation magnetic flux density (Bs) was measured at a magnetic field of 1000 kA / m using a vibrating sample magnetometer (VSM). The coercive force (Hc) was measured at a magnetic field of 5 kA / m using a direct current BH tracer. The surface roughness (Rv and Rz) was measured using a laser microscope.

  In Experimental Examples 1 to 3, the saturation magnetic flux density was set to 1.30 T or higher, to 1.35 T or higher, and to 1.40 T or higher. The coercive force was 3.0 A / m or less, 2.5 A / m or less was better, 2.0 A / m or less was even better, and 1.5 A / m or less was the best. The surface roughness Rv was determined to be 12 μm or less. The surface roughness Rz was determined to be 20 μm or less.

  In the examples shown below, X-ray diffraction measurement, and transmission electron microscope showed that all Fe-based nanocrystals having an average particle diameter of 5 to 30 nm and a crystal structure of bcc were present unless otherwise specified. It was confirmed by observation using Further, it was confirmed by ICP analysis that there was no change in the alloy composition before and after the heat treatment.

  From Table 1, sample Nos. 9 to 12 in which the content of each component was within a predetermined range and the roll contact distance and roll temperature were suitable were all good. In contrast, Sample Nos. 1 to 8, 13 and 14 in which the content of some component was outside the predetermined range deteriorated the surface roughness.

(Experimental example 2)
In Experimental Example 2, the raw metal was weighed so as to have the alloy composition of each Example and Comparative Example shown in the following table, melted by high-frequency heating, and the same conditions as in Experimental Example 1 except that a mother alloy was produced. Carried out.

  Tables 2 to 11 describe examples and comparative examples in which the S content (f) and the Ti content (g) were changed for several combinations of a to e. Note that the type of M is Nb. Examples in which the content of each component was within a predetermined range had good saturation magnetic flux density Bs, coercive force Hc, and surface roughness.

  The comparative example which does not contain S and Ti deteriorated the surface roughness.

  In the comparative example in which the S content (f) is too large, the ribbon before the heat treatment is likely to be composed of a crystalline phase. When the ribbon before the heat treatment was composed of a crystal phase, the coercive force Hc after the heat treatment was remarkably increased. The coercive force Hc was increased even when the ribbon before the heat treatment was made of an amorphous phase.

In the comparative example in which the Ti content ( g ) was too large, the ribbon before the heat treatment was likely to be composed of a crystalline phase, and the coercive force after the heat treatment was significantly increased.

  In Table 12, the examples in which the content of each component is within a predetermined range had good saturation magnetic flux density Bs, coercive force Hc, and surface roughness.

  Sample numbers 235 to 243 in Table 12 describe examples and comparative examples in which the M content (a) was changed. In sample number 235 in which the M content (a) was too small, the ribbon before the heat treatment was composed of a crystalline phase, and the coercive force Hc after the heat treatment was remarkably increased. In sample number 243 in which the M content (a) was too large, the saturation magnetic flux density Bs decreased.

  Sample numbers 244 to 251 in Table 12 describe examples and comparative examples in which the B content (b) was changed. In Sample No. 244 in which the B content (b) was too small, the ribbon before the heat treatment was composed of a crystalline phase, and the coercive force Hc after the heat treatment was significantly increased. In sample number 243 in which the B content (b) was too large, the saturation magnetic flux density Bs decreased.

  Sample numbers 252 to 259 in Table 12 describe examples and comparative examples in which the P content (c) was changed. Sample number 252 in which the content (c) of P was too small had a large coercive force Hc after heat treatment, and the surface roughness deteriorated. In sample number 259 in which the content (c) of P was too large, the saturation magnetic flux density Bs decreased.

  Sample numbers 260 to 274 in Table 12 describe examples and comparative examples in which the Si content (d) and the C content (e) were changed. Sample No. 270 in which the Si content (d) was too large had a large coercive force Hc after the heat treatment. Sample No. 264, in which the C content (e) is too large, had a large coercive force Hc after the heat treatment.

  Tables 13 to 15 are examples in which a part of Fe of sample number 24 was replaced with X1 and / or X2.

  From Table 13 to Table 15, even when a part of Fe was replaced with X1 and / or X2, good characteristics were shown.

  Table 16 is an example identical to sample number 237, 24 or 241 except for the type of M. Sample numbers 237a to 237i are the same as sample number 237, sample numbers 24a to 24i are the same as sample number 24, and sample numbers 241a to 241i are the same as sample number 241.

  Table 16 shows good characteristics even when the type of M is changed.

(Experimental example 3)
In Experimental Example 3, the average particle size of the initial microcrystals and the average particle size of the Fe-based nanocrystalline alloy were changed for the sample number 24 by appropriately changing the molten metal temperature and the heat treatment conditions after the ribbon production. The results are shown in Table 17.

  From Table 17, when the average grain size of the initial microcrystal is 0.3 to 10 nm and the average grain size of the Fe-based nanocrystalline alloy is 5 to 30 nm, it is saturated as compared with the case outside the above range. Both magnetic flux density and coercive force were good.

(Experimental example 4)
Raw material metals were weighed so as to have the alloy compositions of Examples and Comparative Examples shown in Tables 18 to 21 below, and dissolved by high-frequency heating to prepare mother alloys.

  Thereafter, the produced master alloy was heated and melted to form a metal in a molten state at 1250 ° C., and then the roll was rotated at a rotational speed of 25 m / sec. The metal was sprayed onto a roll by a single roll method that was rotated at a thin film to create a ribbon. The material of the roll was Cu.

  The roll was rotated in the direction shown in FIG. Also, by setting the differential pressure between the chamber and the injection nozzle to 105 kPa, the nozzle diameter 5 mm slit, the flow rate 50 g, and the roll diameter φ300 mm, the thickness of the obtained ribbon is 20-30 μm and the width of the ribbon is 4 mm. -5 mm, and the length of the ribbon was set to several tens of meters.

  X-ray diffraction measurement was performed on each obtained ribbon to confirm the presence or absence of crystals having a particle size larger than 30 nm. When there is no crystal having a particle size larger than 30 nm, it is assumed to be composed of an amorphous phase, and when a crystal having a particle size larger than 30 nm is present, it is composed of a crystalline phase. In all examples except for sample number 322, which will be described later, the initial microcrystals had a nanoheterostructure existing in an amorphous state.

  Thereafter, heat treatment was performed on the ribbons of Examples and Comparative Examples under the conditions shown in the table below. Saturation magnetic flux density, coercive force and surface roughness (Rv and Rz) were measured for each ribbon after the heat treatment. The saturation magnetic flux density (Bs) was measured at a magnetic field of 1000 kA / m using a vibrating sample magnetometer (VSM). The coercive force (Hc) was measured at a magnetic field of 5 kA / m using a direct current BH tracer. The surface roughness (Rv and Rz) was measured using a laser microscope.

  In Experimental Examples 4 and 5, the saturation magnetic flux density was 1.50 T or higher. The coercive force was 3.0 A / m or less, 2.5 A / m or less was better, 2.0 A / m or less was even better, and 1.5 A / m or less was the best. The surface roughness Rv was determined to be 12 μm or less. The surface roughness Rz was determined to be 20 μm or less.

  In the examples shown below, X-ray diffraction measurement, and transmission electron microscope showed that all Fe-based nanocrystals having an average particle diameter of 5 to 30 nm and a crystal structure of bcc were present unless otherwise specified. It was confirmed by observation using Further, it was confirmed by ICP analysis that there was no change in the alloy composition before and after the heat treatment.

  From Table 18 to Table 19, all the characteristics were good in Examples in which the content of each component was within a predetermined range. On the other hand, in the comparative example in which the content of some component is outside the predetermined range, one or more of coercive force, saturation magnetic flux density, and surface roughness deteriorated. Furthermore, in the comparative example in which a is too small, the comparative example in which b is too small, and the comparative example in which g is too large, the ribbon before the heat treatment is made of a crystalline phase, and the coercive force Hc after the heat treatment is remarkably increased. Further, the surface roughness sometimes deteriorated.

  Table 20 shows an example in which part of Fe of sample number 410 was replaced with X1 and / or X2.

  From Table 20, even if a part of Fe was replaced with X1 and / or X2, good characteristics were shown.

  Table 21 shows an example in which the M type of the sample number 410 was changed.

  Table 21 shows good characteristics even when the type of M is changed.

(Experimental example 5)
In Experimental Example 5, with respect to Sample No. 410, the average particle size of the initial microcrystals and the average particle size of the Fe-based nanocrystalline alloy were changed by appropriately changing the molten metal temperature and the heat treatment conditions after the ribbon production. The results are shown in Table 20.

  From Table 22, when the average grain size of the initial microcrystals is 0.3 to 10 nm and the average grain size of the Fe-based nanocrystalline alloy is 5 to 30 nm, it is saturated as compared with the case outside the above range. Both magnetic flux density and coercive force were good.

21, 31 ... Nozzle 22, 32 ... Molten metal 23, 33 ... Roll 24, 34 ... Strip 25, 35 ... Chamber 26 ... Stripping gas injection device

Claims (13)

Composition formula _{(Fe (1- (α + β} )) X1 α X2 β) A _{(1- (a + b + c} + d + e + f + g)) M a B b P c Si d C e S f Ti g Tona Ru formed minutes was soft magnetic alloy,
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0 <c ≦ 0.040
0 ≦ d ≦ 0.060
0.0005 <e <0.0050
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
Have a nano-hetero structure that initial fine crystals are present in the amorphous,
0.1 wt% or less der Ru soft magnetic alloy with respect to 100 wt% content of the soft magnetic alloy of the elements other than the elements included in the component.   The soft magnetic alloy according to claim 1, wherein the initial crystallite has an average particle size of 0.3 to 10 nm. Composition formula _{(Fe (1- (α + β} )) X1 α X2 β) a _{(1- (a + b + c} + d + e + f + g)) M a B b P c Si d C e S f Ti g Tona Ru formed minutes was soft magnetic alloy,
X1 is one or more selected from the group consisting of Co and Ni,
X2 is one or more selected from the group consisting of Al, Mn, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, O and rare earth elements,
M is at least one selected from the group consisting of Nb, Hf, Zr, Ta, Mo, W and V;
0.020 ≦ a ≦ 0.14
0.020 <b ≦ 0.20
0 <c ≦ 0.040
0 ≦ d ≦ 0.060
0.0005 <e <0.0050
0 ≦ f ≦ 0.010
0 ≦ g ≦ 0.0010
α ≧ 0
β ≧ 0
0 ≦ α + β ≦ 0.50
And
at least one of f and g is greater than 0;
Have a structure in which the soft magnetic alloy of Fe group nanocrystalline,
0.1 wt% or less der Ru soft magnetic alloy with respect to 100 wt% content of the soft magnetic alloy of the elements other than the elements included in the component.   The soft magnetic alloy according to claim 3, wherein an average particle diameter of the Fe-based nanocrystal is 5 to 30 nm.   The soft magnetic alloy according to claim 1, wherein 0.73 ≦ 1− (a + b + c + d + e + f + g) ≦ 0.95.   The soft magnetic alloy according to claim 1, wherein 0 ≦ α {1− (a + b + c + d + e + f + g)} ≦ 0.40.   The soft magnetic alloy according to claim 1, wherein α = 0.   The soft magnetic alloy according to claim 1, wherein 0 ≦ β {1− (a + b + c + d + e + f + g)} ≦ 0.030.   The soft magnetic alloy according to claim 1, wherein β = 0.   The soft magnetic alloy according to claim 1, wherein α = β = 0.   The soft magnetic alloy according to any one of claims 1 to 10, which has a ribbon shape.   It is a powder form, The soft-magnetic alloy in any one of Claims 1-10.   A magnetic component comprising the soft magnetic alloy according to claim 1.

Images