JP6926992B2 - Manufacturing method of soft magnetic dust core and soft magnetic dust core - Google Patents

Description

The present invention relates to a method for producing a soft magnetic powder magnetic core and a soft magnetic powder magnetic core.

In recent years, low power consumption and high efficiency have been required in electronic, information, communication equipment and the like. Furthermore, the above demands are becoming stronger toward a low-carbon society. Therefore, power supply circuits for electronic, information, and communication equipment are also required to reduce energy loss and improve power supply efficiency. Further, the magnetic core of the porcelain element used in the power supply circuit is required to reduce the core loss (magnetic core loss). If the core loss is reduced, the loss of electric power energy is reduced, and high efficiency and energy saving can be achieved.

Patent Document 1 describes that by changing the particle shape of the powder, a soft magnetic powder having a small core loss and suitable for a magnetic core was obtained. However, at present, there is a demand for a magnetic core having a smaller core loss while maintaining a high resistivity.

Japanese Unexamined Patent Publication No. 2000-30924

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

An object of the present invention is to provide a method for producing a soft magnetic powder magnetic core having a low coercive force and a high specific resistance, and to provide a soft magnetic powder magnetic core.

In order to achieve the above object, the method for producing a soft magnetic dust core according to the present invention is:
A method for producing a soft magnetic powder magnetic core, which comprises a step of obtaining a soft magnetic powder made of a soft magnetic alloy and a step of molding the soft magnetic powder.
The molding temperature in the step of molding the soft magnetic powder is 400 ° C. or higher and 700 ° C. or lower, and the molding pressure is 400 MPa or higher and 2000 MPa or lower.
The soft magnetic alloy contains Fe as a main component, and comprises an Fe composition network phase in which regions having an Fe content of 0.1 at% or more higher than the average composition of the soft magnetic alloy are connected, and the Fe composition network phase is Fe. The maximum point of the Fe content is 2.0 at% or more higher than the average composition of the soft magnetic alloy and the Fe content is 0.1 at% or more higher than the surroundings, and the maximum points are adjacent to each other. When a virtual line connecting points is set, the ^{total virtual line distance per 1 μm 3 of the} soft magnetic alloy is 10 mm to 25 mm, and the average virtual line distance is 6 nm or more and 12 nm or less.

The soft magnetic powder magnetic core produced by the method for producing a soft magnetic powder magnetic core according to the present invention has a low coercive force and a high specific resistance.

The standard deviation of the distance of the virtual line may be 6 nm or less.

The abundance ratio of the virtual line having a distance of 4 nm or more and 16 nm or less may be 80% or more and 100% or less.

The volume ratio of the Fe composition network phase to the entire soft magnetic alloy may be 25 vol% or more and 50 vol% or less.

The content volume ratio of the Fe composition network phase may be 30 vol% or more and 40 vol% or less.

The soft magnetic dust core according to the present invention is a soft magnetic dust core obtained by the above-mentioned production method, and is characterized by having a relative density of 0.90 or more.

It is a photograph which observed the Fe concentration distribution of the soft magnetic alloy in one Embodiment of this invention with a three-dimensional atom probe. It is a photograph of the network structure model which the soft magnetic alloy has in one Embodiment of this invention. It is a schematic diagram of the process of searching for a maximum point. It is a schematic diagram of the state in which the line segment connecting all the maximum points is generated. It is a schematic diagram of the state which divided into the region where the Fe content exceeds the average value and the region below the average value. It is a schematic diagram of the state in which the line segment passing through the region where the Fe content is below the average value is deleted. It is a schematic diagram of the state in which the longest line segment among the line segments forming a triangle is deleted when there is no portion in which the Fe content is less than the average value inside the triangle. It is a schematic diagram of a single roll method. It is a graph which shows the relationship between the coordination number and the maximum score ratio in each composition. It is a soft magnetic powder magnetic core in one embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described.

The method for producing a soft magnetic dust core according to the present embodiment includes at least a step of obtaining a soft magnetic powder made of a soft magnetic alloy and a step of molding the soft magnetic powder.

The soft magnetic alloy is a soft magnetic alloy containing Fe as a main component. Specifically, "containing Fe as a main component" refers to a soft magnetic alloy in which the content of Fe in the entire soft magnetic alloy is 65 atomic% or more.

The composition of the soft magnetic alloy according to the present embodiment is not particularly limited except that Fe is the main component. Examples thereof include Fe-Si-M1-B-Cu-C based soft magnetic alloys and Fe-M2-BC based soft magnetic alloys, but other soft magnetic alloys may also be used.

In the following description, the content of each element of the soft magnetic alloy is 100 atomic% of the whole soft magnetic alloy unless the population parameter is specified.

When a Fe-Si-M1-B-Cu-C based soft magnetic alloy is used, the composition of the Fe-Si-M1-B-Cu-C based soft magnetic alloy is set to Fe _a Cu _b M1 _c Si _{dB. When} expressed as e C _f , it is preferable to satisfy the following equation. By satisfying the following formula, the number of maximum points of the Fe content, which will be described later, tends to increase, and it tends to be easy to obtain a preferable Fe composition network phase. Further, it tends to be easy to obtain a soft magnetic alloy having a low coercive force and a high magnetic permeability. The raw material of the soft magnetic alloy having the following composition is relatively inexpensive. The Fe-Si-M1-B-Cu-C based soft magnetic alloy in the present application also includes a soft magnetic alloy containing f = 0, that is, C is not contained.

a + b + c + d + e + f = 100
0.1 ≤ b ≤ 3.0
1.0 ≤ c ≤ 10.0
4.0 ≤ d ≤ 17.5
7.0 ≤ e ≤ 13.0
0.0 ≤ f ≤ 4.0

The Cu content (b) is preferably 0.1 to 3.0 atomic%, more preferably 0.5 to 1.5 atomic%. Further, the smaller the Cu content, the easier it is to produce a thin band made of a soft magnetic alloy by the single roll method described later.

M1 is one or more selected from transition metal elements and P. Preferably, it is one or more selected from the group consisting of Nb, Ti, Zr, Hf, V, Ta, Mo, P, and Cr. Further, more preferably, Nb and / or P is contained as M1.

The content (c) of M1 is preferably 1.0 to 10.0 atomic%, more preferably 3.0 to 4.0 atomic%.

The Si content (d) is preferably 4.0 to 17.5 atomic%, more preferably 4.0 to 13.5 atomic%.

The content (e) of B is preferably 7.0 to 13.0 atomic%, more preferably 8.0 to 9.0 atomic%.

The C content (f) is preferably 0.0 to 4.0 atomic%. Amorphousness is improved by adding C. When C is not added, the oxidation resistance is excellent.

Fe is, so to speak, the rest of the Fe-Si-M1-B-Cu-C based soft magnetic alloy according to the present embodiment.

When a Fe-M2-BC-based soft magnetic alloy is used, the composition of the Fe-M2-BC-based soft magnetic alloy _{is expressed as Fe α} M2 _β B _γ C _Ω as follows. It is preferable to satisfy the formula. By satisfying the following formula, the number of maximum points of the Fe content, which will be described later, tends to increase, and it tends to be easy to obtain a preferable Fe composition network phase. Further, it tends to be easy to obtain a soft magnetic alloy having a low coercive force and a high magnetic permeability. The raw material of the soft magnetic alloy having the following composition is relatively inexpensive. It is assumed that the Fe-M2-BC-based soft magnetic alloy in the present application also includes a soft magnetic alloy containing Ω = 0, that is, C is not contained.

α + β + γ + Ω = 100
1.0 ≤ β ≤ 14.1
2.0 ≤ γ ≤ 20.0
0.0 ≤ Ω ≤ 4.0

M2 is a transition metal element or P. Preferably, it is one or more selected from the group consisting of Nb, Cu, Zr, Hf, P, and Cr. More preferably, it is one or more selected from the group consisting of Nb, Cu, and P.

The content (β) of M2 is preferably 1.0 to 14.1 atomic%, more preferably 7.0 to 8.7 atomic%.

Further, the content of Cu contained in M2 is preferably 0.0 to 0.7 atomic% with the entire soft magnetic alloy as 100 atomic%.

The content (γ) of B is preferably 2.0 to 20.0 atomic%, more preferably 4.5 to 18.0 atomic%, and is 8.0 to 9.0 atomic%. It is more preferable to have. The smaller the B content, the lower the amorphousness tends to be. The larger the B content, the smaller the number of maximum points described later.

The C content (Ω) is preferably 0.0 to 4.0 atomic%. Amorphousness tends to be improved by adding C. The larger the C content, the smaller the number of maximum points described later. Further, when C is not added, the oxidation resistance is excellent.

Here, the Fe composition network phase contained in the soft magnetic alloy according to the present embodiment will be described.

The Fe composition network phase is a phase in which the Fe content is 0.1 at% or more higher than the average composition of the soft magnetic alloy. When the Fe concentration distribution of the soft magnetic alloy according to the present embodiment is observed with a three-dimensional atom probe (hereinafter, may be referred to as 3DAP) at a thickness of 5 nm, the portion having a high Fe content is network-like as shown in FIG. The state of distribution can be observed. FIG. 2 is a schematic diagram showing the distribution in three dimensions.

In the conventional Fe-containing soft magnetic alloy, a plurality of portions having a high Fe content have a spherical shape or a substantially spherical shape, respectively, and are present separately through the portions having a low Fe content. The soft magnetic alloy according to the present embodiment is characterized in that portions having a high Fe content are connected and distributed in a network shape as shown in FIG.

The aspect of the Fe composition network phase can be quantified by measuring the total virtual line distance and the average virtual line distance described later.

Hereinafter, a method of calculating the total virtual line distance and the average virtual line distance will be described by explaining the analysis procedure of the Fe composition network phase in the present embodiment with reference to the drawings.

First, the definition of the maximum point of the Fe composition network phase and the method of confirming the maximum point will be described. The maximum point of the Fe composition network phase is that the Fe content is 2.0 at% or more higher than the average composition of the soft magnetic alloy and the Fe content is 0.1 at% or more higher than the surroundings. The point is that the Fe content is higher than that of the surroundings.

A cube having a side length of 40 nm is set as a measurement range, and the cube is divided into cube-shaped grids having a side length of 1 nm. That is, there are 40 × 40 × 40 = 64,000 grids in one measurement range.

Next, the Fe content contained in each grid is evaluated. Then, the average value of the Fe content in all the grids (hereinafter, may be referred to as a threshold value) is calculated. The average value of the Fe content is substantially the same as the value calculated from the average composition of each soft magnetic alloy.

Next, the grid whose Fe content is 2.0 at% or more higher than the threshold value and whose Fe content is 0.1 at% or more higher than all the adjacent grids is set as the maximum point. FIG. 3 shows a model showing a process of searching for the maximum point. The numbers described inside each grid 10 represent the Fe content contained in each grid. A grid having an Fe content equal to or higher than the Fe content of all adjacent grids 10b is defined as a maximum point 10a. At the maximum point 10a, the Fe content is 2.0 at% or more higher than the threshold value.

Further, in FIG. 3, eight adjacent grids 10b are shown for one maximum point 10a, but in reality, there are nine adjacent grids 10b in front of and behind the maximum point 10a in FIG. There are one by one. That is, there are 26 adjacent grids 10b for one maximum point 10a.

Further, with respect to the grid 10 located at the end of the measurement range, it is considered that a grid having an Fe content of 0 exists outside the measurement range.

Next, as shown in FIG. 4, a line segment connecting all the maximum points 10a included in the measurement range is generated. Moreover, this line segment is a virtual line. When connecting virtual lines, connect the center of each grid. In FIGS. 4 to 7, for convenience of explanation, the maximum point 10a is indicated by a circle. The number written inside the circle is the Fe content.

Next, as shown in FIG. 5, a region (= Fe composition network phase) 20a having an Fe content higher than the threshold value by 0.1 at% or more and a region 20b having an Fe content below the threshold value are separated. Then, as shown in FIG. 6, the virtual line passing through the area 20b is deleted.

Further, the virtual line connecting the maximum point of the grit existing on the outermost surface within the measurement range of 40 nm × 40 nm × 40 nm and the maximum point of another grid existing on the same outermost surface is deleted. Further, when calculating the virtual line average distance and the virtual line standard deviation, which will be described later, the virtual line passing through the maximum point of the grid existing on the outermost surface is excluded from the calculation.

Next, as shown in FIG. 7, when the virtual line is a part forming a triangle and there is no region 20b inside the triangle, the longest virtual line among the three virtual lines forming the triangle is used. Delete one line. Finally, when the maximum points are on adjacent grids, the virtual line connecting the maximum points is deleted.

The total virtual line distance is calculated by summing the lengths of the virtual lines remaining in the measurement range. Further, the number of virtual lines is calculated, and the average virtual line distance, which is the distance per virtual line, is calculated.

It is assumed that the Fe composition network phase also includes a maximum point having no virtual line and a region having an Fe content higher than the threshold value existing around the maximum point having no virtual line.

By performing the measurements shown above several times in different measurement ranges, the accuracy of the calculated results can be made sufficiently high. Preferably, the measurement is performed three times or more in different measurement ranges.

The Fe composition network phase of the soft magnetic alloy according to the present embodiment has a total virtual line distance of 10 mm or more and 25 mm or less per ^{1 μm 3 of the soft magnetic alloy.} The average distance of virtual lines, that is, the average distance of virtual lines is 6 nm or more and 12 nm or less.

The soft magnetic alloy according to the present embodiment has a Fe composition network phase in which the total virtual line distance and the average virtual line distance are within the above ranges, so that the coercive force is low and the magnetic permeability is high, and the soft magnetism is particularly high at high frequencies. A soft magnetic alloy having excellent properties can be obtained.

Preferably, the standard deviation of the distance of the virtual line is 6 nm or less.

Preferably, the abundance ratio of the virtual line having a distance of 4 nm or more and 16 nm or less is 80% or more.

Further, the volume ratio of the Fe composition network phase to the entire soft magnetic alloy (the threshold value in the total of the region 20a having an Fe content higher than the threshold value by 0.1 at% or more and the region 20b having an Fe content equal to or lower than the threshold value). The volume ratio of the region 20a having an Fe content higher than 0.1 at% or more is preferably 25 vol% or more and 50 vol% or less, and more preferably 30 vol% or more and 40 vol% or less.

Comparing the case of Fe-Si-M1-B-Cu-C based soft magnetic alloy and the case of Fe-M2-BC based soft magnetic alloy, the total virtual line distance is Fe-M2-BC. The soft magnetic alloy of the system tends to be longer. Further, the average virtual line distance tends to be longer in the case of the Fe-Si-M1-B-Cu-C based soft magnetic alloy. FIG. 9 is a schematic diagram showing the relationship between the length of the virtual line and the ratio of the number of virtual lines in the soft magnetic alloy of the Fe-Si-M1-B-Cu-C system and the soft magnetic alloy of the Fe-M2-BC system. Is.

Comparing the case of the Fe-Si-M1-B-Cu-C based soft magnetic alloy with the case of the Fe-M2-BC based soft magnetic alloy, the coercive force is Fe-Si-M1-B. -Cu-C based soft magnetic alloys tend to be lower.

The method for producing the soft magnetic powder made of the soft magnetic alloy according to the present embodiment is not particularly limited. For example, there is a method of producing a soft magnetic alloy strip according to the present embodiment by a single roll method and crushing the soft magnetic alloy strip.

In the single roll method, first, the pure metal of each metal element contained in the soft magnetic alloy strip is prepared, and weighed so as to have the same composition as the soft magnetic alloy strip obtained by the single roll method. Then, the pure metal of each metal element is melted and mixed to prepare a mother alloy. The method for melting the pure metal is not particularly limited, but for example, there is a method in which the pure metal is evacuated in a chamber and then melted by high-frequency heating. The mother alloy and the finally obtained soft magnetic alloy strip have the same composition.

Next, the produced mother alloy is heated and melted to obtain a molten metal (bath). The temperature of the molten metal is not particularly limited, but can be, for example, 1200 to 1500 ° C.

A schematic diagram of the apparatus used in the single roll method is shown in FIG. In the single roll method according to the present embodiment, the molten metal 32 is injected and supplied from the nozzle 31 to the roll 33 rotating in the direction of the arrow inside the chamber 35, so that the thin band 34 is formed in the rotation direction of the roll 33. Manufactured. In this embodiment, the material of the roll 33 is not particularly limited. For example, a roll made of Cu is used.

In the single roll method, the thickness of the thin band obtained mainly by adjusting the rotation speed of the roll 33 can be adjusted. For example, the distance between the nozzle 31 and the roll 33 and the temperature of the molten metal can be adjusted. The thickness of the thin band obtained by doing so can also be adjusted. The thickness of the thin band is not particularly limited, but can be, for example, 15 to 30 μm.

At the time before the heat treatment described later, the thin band is preferably amorphous. The above-mentioned preferable Fe composition network phase can be obtained by subjecting the amorphous thin band to a heat treatment described later.

There is no particular limitation on the method for confirming whether or not the thin band of the soft magnetic alloy before the heat treatment is amorphous. Here, the fact that the thin band is amorphous means that the thin band does not contain crystals. For example, the presence or absence of crystals having a particle size of about 0.01 to 10 μm can be confirmed by ordinary X-ray diffraction measurement. Further, when crystals are present in the above amorphous substance but the volume ratio of the crystals is small, it is determined that there are no crystals by ordinary X-ray diffraction measurement. The presence or absence of crystals in this case is confirmed, for example, by obtaining a selected area diffraction image, a nanobeam diffraction image, a bright field image or a high resolution image of a sample sliced by ion milling using a transmission electron microscope. can. When a selected area diffraction image or a nanobeam diffraction image is used, ring-shaped diffraction is formed when the diffraction pattern is amorphous, whereas when it is not amorphous, diffraction spots due to the crystal structure are formed. Is formed. In the case of using a bright-field image or a high resolution image can confirm the presence or absence of crystals by observing visually at a magnification 1.00 × ^{10 5} ~3.00 × ¹⁰ 5 times. In the present specification, when it can be confirmed that a crystal is present by ordinary X-ray diffraction measurement, it is defined as "there is a crystal", and although it cannot be confirmed by ordinary X-ray diffraction measurement that a crystal is present, it is possible to confirm that there is a crystal by ion milling. If it can be confirmed that crystals are present on the sliced sample by obtaining a selected area diffraction image, a nanobeam diffraction image, a bright field image or a high resolution image using a transmitted electron microscope, "microcrystals are present. There is. "

Here, the present inventors can easily make the thin band of the soft magnetic alloy before the heat treatment amorphous by appropriately controlling the temperature of the roll 33 and the vapor pressure inside the chamber 35, and have a preferable Fe composition after the heat treatment. We found that it became easier to obtain the network phase. Specifically, the temperature of the roll 33 is set to 50 to 70 ° C., preferably 70 ° C., and the vapor pressure inside the chamber 35 is set to 11 hPa or less, preferably 4 hPa or less by using Ar gas whose dew point is adjusted. It has been found that the thin band of the soft magnetic alloy can be easily made amorphous.

Conventionally, in the single roll method, it is considered preferable to improve the cooling rate and quench the molten metal 32, and it is possible to improve the cooling rate by widening the temperature difference between the molten metal 32 and the roll 33. It was considered preferable. Therefore, it has been considered that the temperature of the roll 33 is usually preferably about 5 to 30 ° C. However, the present inventors uniformly cool the molten metal 32 by raising the temperature of the roll 33 to 50 to 70 ° C., which is higher than that of the conventional single roll method, and further setting the vapor pressure inside the chamber 35 to 11 hPa or less. , It has been found that the thin band of the obtained soft magnetic alloy before heat treatment can be easily made uniform and amorphous. There is no particular lower limit of the vapor pressure inside the chamber. The dew point-adjusted argon may be filled to reduce the vapor pressure to 1 hPa or less, or the vapor pressure may be set to 1 hPa or less in a state close to vacuum. Further, when the vapor pressure becomes high, it becomes difficult to make the thin band before the heat treatment amorphous, and even if it becomes amorphous, it becomes difficult to obtain the above-mentioned preferable Fe composition network phase after the heat treatment described later.

The above-mentioned preferable Fe composition network phase can be obtained by heat-treating the obtained thin band 34. At this time, if the thin band 34 is completely amorphous, it becomes easy to obtain the above-mentioned preferable Fe composition network phase.

The heat treatment conditions are not particularly limited. Preferred heat treatment conditions differ depending on the composition of the soft magnetic alloy. Generally, the preferable heat treatment temperature is about 500 to 600 ° C., and the preferable heat treatment time is about 0.5 to 10 hours. However, depending on the composition, there may be a preferable heat treatment temperature and heat treatment time outside the above range.

Next, a crushing step of crushing the obtained soft magnetic alloy to obtain a soft magnetic powder will be described, but the crushing step can be performed by any method.

The pulverization step can be performed in two steps, for example, a coarse pulverization step of pulverizing until the particle size is about several hundred μm to several mm, and a fine pulverization step of pulverizing until the particle size is about several μm. .. However, it may be carried out in one step of the pulverization step.

In the coarse pulverization step, each soft magnetic alloy is coarsely pulverized until the particle size is about several hundred μm to several mm. As a result, a coarsely pulverized powder of a soft magnetic alloy is obtained. Coarse pulverization can be performed by any method. For example, after hydrogen is occluded in a soft magnetic alloy, hydrogen is released based on the difference in the amount of hydrogen occluded between different phases, and dehydrogenation is performed to cause self-destructive crushing (hydrogen storage crushing). It can be carried out.

In addition to the method using hydrogen storage crushing as described above, the rough crushing step is performed by a method using a rough crusher such as a stamp mill, a jaw crusher, or a brown mill in an inert gas atmosphere. May be good.

After coarsely pulverizing the soft magnetic alloy, the obtained coarsely pulverized powder of the soft magnetic alloy is finely pulverized until the average particle size becomes about several μm. As a result, a soft magnetic powder is obtained. By further pulverizing the coarsely pulverized powder, a finely pulverized powder having an average particle size of 0.5 μm or more and 300 μm or less may be obtained.

The pulverization step is carried out using a pulverizer such as a jet mill or a bead mill while appropriately adjusting conditions such as pulverization time. A jet mill releases a high-pressure inert gas (for example, N ₂ gas) from a narrow nozzle to generate a high-speed gas flow, and this high-speed gas flow accelerates the coarsely pulverized powder of a soft magnetic alloy to make it soft magnetic. This is a dry crushing method in which coarsely crushed powders of an alloy collide with each other or collide with a target or a container wall to crush the powder.

In particular, when a soft magnetic powder having a fine particle size is to be obtained by using a jet mill, the surface of the crushed powder is very active, so that the crushed soft magnetic powders reaggregate with each other and adhere to the container wall. Adhesion is likely to occur and the yield tends to be low. Therefore, when the coarsely pulverized powder of the soft magnetic alloy is finely pulverized, a pulverizing aid such as zinc stearate or oleate amide is added to prevent the soft magnetic powders from reaggregating with each other and adhering to the container wall. Therefore, the soft magnetic powder can be obtained in a high yield. Further, by adding the pulverizing aid in this way, it is possible to obtain a finely pulverized powder that is easily oriented when used for molding. The amount of the pulverizing aid added varies depending on the particle size of the pulverized powder and the type of the pulverizing aid to be added, but may be about 0.1% to 1% by mass with respect to the pulverized powder.

As a method other than the dry pulverization method such as a jet mill, there is a wet pulverization method. As the wet pulverization method, for example, a bead mill in which beads having a small diameter are used and stirred at high speed can be used. Further, after dry pulverization with a jet mill, multi-stage pulverization may be further performed by wet pulverization with a bead mill.

Further, as a method for obtaining a soft magnetic powder made of a soft magnetic alloy according to the present embodiment, in addition to the above-mentioned single roll method, for example, a water atomizing method or a gas atomizing method is used to obtain a powder of the soft magnetic alloy according to the present embodiment. There is a method of pulverizing the powder as needed. Hereinafter, the gas atomizing method will be described.

In the gas atomizing method, a molten alloy at 1200 to 1500 ° C. is obtained in the same manner as in the single roll method described above. Then, the molten alloy is injected in the chamber to prepare a powder.

At this time, by setting the gas injection temperature to 50 to 100 ° C. and setting the vapor pressure in the chamber to 4 hPa or less, it becomes easy to finally obtain the above-mentioned preferable Fe composition network phase.

After preparing the powder by the gas atomization method, heat treatment is performed at 500 to 650 ° C. for 0.5 to 10 minutes to diffuse the elements while preventing the powders from sintering each other and coarsening the powders. It promotes, the thermodynamic equilibrium state can be reached in a short time, strain and stress can be removed, and the Fe composition network phase can be easily obtained. Then, a soft magnetic powder having good soft magnetic properties can be obtained particularly in a high frequency region.

Further, the powder after the heat treatment may be used as it is as a soft magnetic powder, or the powder after the heat treatment may be coarsely pulverized and / or finely pulverized as necessary to obtain a soft magnetic powder.

A soft magnetic powder can be obtained by the above method. When the soft magnetic alloy before pulverization has an Fe composition network phase, the soft magnetic powder after pulverization also has the same Fe composition network phase as the soft magnetic alloy before pulverization.

Hereinafter, a step of molding the obtained soft magnetic powder will be described.

The soft magnetic powder having the Fe composition network phase described above is easily deformed because the Fe composition network phase is relatively soft. Therefore, a powder magnetic core having a high density and a low coercive force can be obtained by a method in which a soft magnetic powder having an Fe composition network phase is filled in a mold and then molded at a high pressure while heating.

First, the binder and the additive are mixed with the soft magnetic powder before filling the mold with the soft magnetic powder having the Fe composition network phase.

Examples of the method of obtaining the magnetic core from the soft magnetic powder include a method of appropriately mixing with a binder and an additive and then molding using a mold. Further, the surface of the soft magnetic powder may be subjected to an oxidation treatment, an insulating film or the like before being mixed with the binder and the additive. The specific resistance is improved, and a soft magnetic dust core suitable for a higher frequency band can be obtained.

The type of binder is arbitrary. For example, a silicone resin can be used. The mixing ratio of the soft magnetic powder and the binder is arbitrary. For example, 1 to 10% by mass of binder is mixed with 100% by mass of soft magnetic powder.

The type of additive is arbitrary. It is preferable to use an additive having an appropriate softening point according to the heating temperature (molding temperature) during molding described later. As the additive, for example, glass, oxide and the like can be used. As the glass, for example, phosphoric acid-based glass, bismuth-based glass, borosilicate-based glass, vanadate-based glass and the like can be used. As the oxide, for example, bismuth oxide, vanadium oxide and the like can be used. The mixing ratio of the soft magnetic powder and the additive is arbitrary. For example, 0.05 to 20% by mass of the additive is mixed with 100% by mass of the soft magnetic powder.

In the method for producing a soft magnetic dust core according to the present embodiment, it is important to perform compression molding at a high temperature and high pressure within a predetermined range at the time of molding. When the soft magnetic powder has the above-mentioned Fe composition network phase, it is easily deformed as compared with the conventional soft magnetic powder. Therefore, when a binder and an additive are added to the above-mentioned soft magnetic powder having the Fe composition network phase and compression molding is performed at high temperature and high pressure, the density is higher and better than that of the conventional soft magnetic powder magnetic core. It is possible to manufacture a soft magnetic dust core having various magnetic properties. The high density here specifically means a relative density of 0.90 or more. More preferably, the relative density is 0.95 or more. The relative density is the ratio of the actual density to the theoretical density, and the theoretical density is calculated by using the Archimedes method for soft magnetic powder.

Specifically, the molding temperature is 400 ° C. or higher and 700 ° C. or lower, and the molding pressure is 400 MPa or higher and 2000 MPa or lower. When the molding temperature is less than 400 ° C., the relative density is low. When the molding temperature exceeds 700 ° C., a high coercive magnetic force is obtained. Further, when the molding pressure is less than 400 MPa, the relative density becomes low. When the molding pressure is more than 2000 MPa, the coercive force is high.

The molding temperature is preferably 10 ° C. or higher and 100 ° C. or lower, which is higher than the softening point of the above-mentioned additive. In other words, it is preferable to select an additive having a softening point that is 10 ° C. to 100 ° C. lower than the molding temperature.

A magnetic field can be applied to the soft magnetic powder magnetic core at the same time as the step of molding the soft magnetic powder or after molding. The magnitude of the applied magnetic field is arbitrary.

The soft magnetic dust core according to the present embodiment may have an arbitrary shape. For example, the toroidal shape shown in FIG. 10 can be used. Further, the size of the soft magnetic dust core is not particularly limited.

Further, the soft magnetic dust core may be further heat-treated for strain removal. By removing the strain, the core loss is reduced and the usefulness is increased.

Further, an inductance component can be obtained by winding the soft magnetic dust core. There are no particular restrictions on the winding method and the manufacturing method of the inductance component. For example, a method of winding the winding around the magnetic core manufactured by the above method for at least one turn or more can be mentioned.

Further, the inductance component may be manufactured by molding and integrating the winding coil and the soft magnetic powder in a mold. In this case, it is easy to obtain an inductance component corresponding to a high frequency and a large current.

Here, when manufacturing an inductance component using a soft magnetic powder, it is preferable to use a soft magnetic powder having a maximum particle size of 45 μm or less in a sieve diameter and a central particle size (D50) of 30 μm or less, which has excellent Q characteristics. It is preferable to obtain. In order to make the maximum particle size 45 μm or less in the sieve diameter, a sieve having a mesh size of 45 μm may be used, and only the soft magnetic powder passing through the sieve may be used.

The Q value in the high frequency region tends to decrease as the soft magnetic powder having a larger maximum particle size is used. Especially when the soft magnetic powder having a maximum particle size exceeding 45 μm in the sieve diameter is used, the Q value in the high frequency region tends to decrease. May drop significantly. However, when the Q value in the high frequency region is not emphasized, a soft magnetic powder having a large variation can be used. Since the soft magnetic powder having a large variation can be produced at a relatively low cost, it is possible to reduce the cost when the soft magnetic powder having a large variation is used.

There is no particular limitation on the use of the dust core according to the present embodiment. For example, it can be suitably used as a magnetic core for an inductor, particularly a power inductor.

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

(Single roll method)
The pure metal materials were weighed so that the mother alloy having the composition shown in Table 1 below could be obtained. Then, after evacuating in the chamber, it was melted by high frequency heating to prepare a mother alloy.

Then, the prepared mother alloy was heated and melted to obtain a metal in a molten state at 1300 ° C., and then the metal was injected onto the roll by a single roll method under a specified roll temperature and a specified steam pressure to prepare a thin band. Further, the thickness of the thin band obtained by appropriately adjusting the rotation speed of the roll was set to 20 μm. Next, each of the prepared strips was heat-treated to obtain a veneer-shaped sample.

In this example, as shown in Table 1, each sample was prepared by changing the roll temperature, vapor pressure, and heat treatment conditions. The vapor pressure was adjusted by using Ar gas whose dew point was adjusted.

In addition, X-ray diffraction measurement was performed on each soft magnetic alloy strip before the heat treatment to confirm the presence or absence of crystals. Furthermore, the presence or absence of microcrystals was confirmed by observing a selected area diffraction image and a bright field image at a magnification of 300,000 using a transmission electron microscope. Then, it was confirmed whether the thin bands of each Example and Comparative Example were amorphous without crystals and microcrystals, and whether crystals or microcrystals were present. The results are shown in Table 1.

Next, the soft magnetic alloy strip was heat-treated under the conditions shown in Table 1.

Further, for each soft magnetic alloy strip after the heat treatment, the total virtual line distance, the virtual line average distance, and the virtual line standard deviation were measured using a 3DAP (three-dimensional atom probe). Furthermore, the abundance ratio of virtual lines having a length of 4 to 16 nm and the volume ratio of the Fe network composition phase were measured. The results are shown in Table 1. The sample described as "<1" in the total virtual line distance column is a sample in which no virtual line exists between the Fe maximum point and the Fe maximum point. However, although there is no grid in which the Fe content is 2.0 at% or more higher than the threshold value and the Fe content is 0.1 at% or more higher than itself, the Fe content is equal to that of itself (of the Fe content). If there is a grid (with a difference of less than 0.1 at%), it may be considered that an extremely short virtual line exists between the two grids when calculating the total virtual line distance. be. As a result, the total virtual line distance may be 0.0001 mm / μm ³ . Therefore, in the case where the application is a virtual line total distance is 0 mm / [mu] m ^3, as further comprising a case which is to be 0.0001 mm / [mu] m ^3, and "<1" to the virtual line total distance column It is described. When calculating the virtual line average distance and the virtual line standard deviation, it is calculated assuming that such an extremely short virtual line does not exist.

<Crushing process>
Each soft magnetic alloy strip described in Table 1 was crushed to obtain a soft magnetic powder. Hydrogen gas was occluded by flowing hydrogen gas through each soft magnetic alloy strip at room temperature for 1 hour. Next, the atmosphere was switched to Ar gas, dehydrogenation treatment was performed at 400 ° C. to 600 ° C. for 1 hour, and the raw material alloy was hydrogen pulverized. Further, after cooling, a sieve was used to prepare a powder having a particle size of 425 μm or less. From hydrogen pulverization to the molding step described later, a low oxygen atmosphere with an oxygen concentration of less than 200 ppm was always used.

Next, 0.1% oleic acid amide by mass ratio was added as a pulverization aid to the powder after hydrogen pulverization, and the mixture was mixed.

Then, it was finely pulverized in a nitrogen stream using a collision plate type jet mill device to obtain a soft magnetic powder having an average particle size of 20 to 30 μm. The average particle size is the average particle size D50 measured by a laser diffraction type particle size distribution meter.

X-ray diffraction measurement was performed on each soft magnetic powder to confirm the presence or absence of crystals. Furthermore, the presence or absence of microcrystals was confirmed by observing a selected area diffraction image and a bright field image at a magnification of 300,000 using a transmission electron microscope. Furthermore, using a 3DAP (three-dimensional atom probe), the total virtual line distance, the virtual line average distance, and the virtual line standard deviation were measured. Furthermore, the abundance ratio of virtual lines having a length of 4 to 16 nm and the volume ratio of the Fe network composition phase were measured. The test results for the soft magnetic powder were the same as those for the soft magnetic alloy strip before pulverization shown in Table 1.

<Molding process>
The obtained soft magnetic powder, silicone resin and additives were mixed and kneaded using a kneader. SR2414 manufactured by Toray Industries, Inc. was used as the silicone resin. As the additive, the types shown in Table 2 below were used. The phosphoric acid-based glass used had a softening point of 350 ° C. The bismuth-based glass used had a softening point of 480 ° C. The borosilicate glass used had a softening point of 550 ° C. Further, the total of the soft magnetic powder, the silicone resin and the additive was set to 100 wt%, the content of the silicone resin was 1.2 wt%, and the content of the additive was 0.5 wt%.

Next, the powder magnetic core precursor obtained by the above kneading was molded using a mold at the molding pressure and molding temperature shown in Table 2 below, and the disk shape (dimensions = diameter 10.0 mm × thickness). A powder magnetic core of 4.0 mm) was prepared. Then, the coercive force, resistivity and relative density of the prepared dust core were measured. The results are shown in Table 2 below.

The coercive force was measured with respect to the dust core using an Hc meter (K-Hc1000 type manufactured by Tohoku Steel Co., Ltd.). Was measured using. The results are shown in Table 2 below. The lower the coercive force, the more preferable.

The specific resistance was measured by applying In-Ga electrodes on both sides of the dust core and measuring the DC resistance value (unit: Ωm). The measurement was carried out using an IR meter (SUPER MEGOHMMETER MODEL SM-5E manufactured by TOA Electronics). In this example, the case of 1000 Ωm or more was regarded as good. In Table 2 below, the case where the specific resistance is 1000 Ωm or more is evaluated as ◯, and the case where the specific resistance is less than 1000 Ωm is evaluated as ×.

For the measurement of the relative density, the density of the dust core was calculated from the size and weight of the dust core, and the density of the dust core with respect to the theoretical density was taken as the relative density. In this example, the relative density was good at 0.90 (90%) or more. The results are shown in Table 2 below.

From Tables 1 and 2, in each example in which the soft magnetic alloy strip had a predetermined Fe composition network phase and the molding step was performed at a molding pressure and a molding temperature within a predetermined range, the specific resistance and the specific resistance and The relative density showed a good value.

Sample No. No. 2 is sample No. 2 except that the soft magnetic alloy strip does not have a predetermined Fe composition network phase. Sample No. 2 under the same conditions as No. 2. The coercive force decreased as compared with 1.

Sample No. 3 to 8 are Examples and Comparative Examples carried out under the same conditions except that the state of the Fe composition network phase was changed by changing the vapor pressure and the heat treatment time in the chamber. Sample No. having a predetermined Fe composition network phase. Sample Nos. 4 to 8 do not have a predetermined Fe composition network phase. The coercive force decreased as compared with 3.

Sample No. Reference numerals 9 to 13 and 13a are Examples and Comparative Examples carried out under the same conditions except that the molding pressure and the molding temperature were changed. Sample No. Even if the soft magnetic alloy strip has a predetermined Fe composition network phase as in 9 and 13a, if the forming pressure and the forming temperature are out of the predetermined range, the coercive force, resistivity and relative density One of them got worse.

Sample No. No. 15 is sample No. 15 except that the soft magnetic alloy strip does not have a predetermined Fe composition network phase. Sample No. 15 under the same conditions as No. 15. The coercive force was reduced as compared with 14. Furthermore, the sample No. Even if the soft magnetic alloy strip has a predetermined Fe composition network phase as in 15a and 15b, if the forming pressure and the forming temperature are out of the predetermined range, the coercive force, resistivity and relative density One of them got worse.

Sample No. No. 17 is sample No. 17 except that the soft magnetic alloy strip does not have a predetermined Fe composition network phase. Sample No. 17 under the same conditions as No. 17. The coercive force was reduced as compared with 16. Furthermore, the sample No. Even if the soft magnetic alloy strip has a predetermined Fe composition network phase as in 17a and 17b, if the forming pressure and the forming temperature are out of the predetermined range, the coercive force, resistivity and relative density One of them got worse.

(Gas atomization method)
The pure metal materials were weighed so as to obtain the mother alloy having the composition shown in Table 3 below. Then, after evacuating in the chamber, it was melted by high frequency heating to prepare a mother alloy.

Then, the prepared mother alloy was heated and melted to obtain a metal in a molten state at 1300 ° C., and then the metal was sprayed under the conditions shown in Table 3 below by a gas atomizing method to prepare a powder. Specifically, the gas injection temperature and the vapor pressure in the chamber are changed to change the sample No. 18-21 were made. The vapor pressure was adjusted by using Ar gas whose dew point was adjusted.

X-ray diffraction measurement was performed on each powder before the heat treatment, and the presence or absence of crystals was confirmed. Furthermore, the selected area diffraction image and the bright field image were observed with a transmission electron microscope. As a result, the sample No. It was confirmed that each of the powders 19 and 21 had no crystals and was completely amorphous. On the other hand, sample No. It was confirmed that microcrystals were present in each of the powders 18 and 20.

Then, each of the obtained powders was heat-treated under the conditions shown in Table 3 below, molded under the conditions shown in Table 4 below, and then the coercive force, resistivity and relative density were measured. Then, various measurements were made on the Fe composition network. In Table 4 below, the case where the specific resistance is 1000 Ωm or more is evaluated as ◯, and the case where the specific resistance is less than 1000 Ωm is evaluated as ×. In this example, the relative density was good at 0.90 (90%) or more. The results are shown in Table 4 below.

Sample No. In 19 and 21, a good Fe network was formed by appropriately heat-treating the completely amorphous powder. However, the sample No. which has an excessively high vapor pressure of 25 hPa. In the comparative examples of 18 and 20, since microcrystals are present in the powder before the heat treatment, the total virtual line distance and the average virtual line distance after the heat treatment are small, a preferable Fe composition network cannot be formed, and the coercive force is high. rice field. Also, the relative density became low.

10 ... Grid 10a ... Maximum point 10b ... Adjacent grid 20a ... Region with Fe content 0.1 at% or more higher than the threshold 20b ... Region with Fe content below the threshold 31 ... Nozzle 32 ... Molten metal 33 ... Roll 34 … Thin band 35… Chamber

Claims (5)

A method for producing a soft magnetic powder magnetic core, which comprises a step of obtaining a soft magnetic powder made of a soft magnetic alloy and a step of molding the soft magnetic powder.
The molding temperature in the step of molding the soft magnetic powder is 400 ° C. or higher and 700 ° C. or lower, and the molding pressure is 400 MPa or higher and 2000 MPa or lower.
The soft magnetic alloy contains Fe as a main component, and comprises an Fe composition network phase in which regions having an Fe content of 0.1 at% or more higher than the average composition of the soft magnetic alloy are connected, and the Fe composition network phase is Fe. The maximum point of the Fe content is 2.0 at% or more higher than the average composition of the soft magnetic alloy and the Fe content is 0.1 at% or more higher than the surroundings, and the maximum points are adjacent to each other. in case of setting a virtual line connecting the points, the imaginary line total distance per soft magnetic alloy 1 [mu] m ³ is at 10mm or more 25mm or less, the average distance imaginary line Ri der than 12nm or less 6 nm,
The soft magnetic alloy is a Fe-Si-M1-B-Cu-C based soft magnetic alloy or a Fe-M2-BC based soft magnetic alloy.
When the soft magnetic alloy is a Fe-Si-M1-B-Cu-C based soft magnetic alloy, M1 is a group consisting of Nb, Ti, Zr, Hf, V, Ta, Mo, P and Cr. in the one or more kinds selected, if the composition of the Fe-Si-M1-B- Cu-C -based soft magnetic alloy is expressed as _{Fe a Cu b M1 c Si d} B e C f,
a + b + c + d + e + f = 100
0.1 ≤ b ≤ 3.0
1.0 ≤ c ≤ 10.0
4.0 ≤ d ≤ 17.5
7.0 ≤ e ≤ 13.0
0.0 ≤ f ≤ 4.0
The filling,
When the soft magnetic alloy is the Fe-M2-BC based soft magnetic alloy, M2 is one or more selected from the group consisting of Nb, Cu, Zr, Hf, P, and Cr. When the composition of the Fe-M2-BC-based soft magnetic alloy is expressed _{as Fe α} M2 _β B _γ C _Ω,
α + β + γ + Ω = 100
1.0 ≤ β ≤ 14.1
2.0 ≤ γ ≤ 20.0
0.0 ≤ Ω ≤ 4.0
A method for producing a soft magnetic powder magnetic core, which is characterized by satisfying the above conditions. The method for producing a soft magnetic dust core according to claim 1, wherein the standard deviation of the distance of the virtual line is 6 nm or less. The method for producing a soft magnetic dust core according to claim 1 or 2, wherein the abundance ratio of the virtual line having a distance of 4 nm or more and 16 nm or less is 80% or more and 100% or less. The method for producing a soft magnetic dust core according to any one of claims 1 to 3, wherein the volume ratio of the Fe composition network phase to the entire soft magnetic alloy is 25 vol% or more and 50 vol% or less. The method for producing a soft magnetic powder magnetic core according to any one of claims 1 to 4, wherein the content volume ratio of the Fe composition network phase is 30 vol% or more and 40 vol% or less.

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