JP2008231534A - Soft magnetic thin band, magnetic core, and magnetic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soft magnetic thin band in which the squareness of magnetic flux density-a magnetization curve is high in a relatively low magnetic field region, particularly, of ≤500 A/m. <P>SOLUTION: As the soft magnetic thin band, the one having a thickness of ≤100 μm, having a mother phase texture where crystal grains with a crystal grain size of ≤60 nm (excluding zero) are dispersed into an amorphous phase in ≥30% by a volume fraction, and also having an amorphous layer on the surface side of the mother phase texture is used. As the soft magnetic thin band, the one expressed by compositional formula: Fe<SB>100-x-y</SB>Cu<SB>x</SB>X<SB>y</SB>(wherein, X denotes one or more kinds of elements selected from B, Si, S, C, P, Al, Ge, Ga and Be and, by atom%, 0≤x≤5 and 10≤y≤24 are satisfied) is preferably used. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  Soft magnetic ribbon with high saturation magnetic flux density and good squareness used in various transformers, laser power supplies, pulse power magnetic components for accelerators, various reactors, noise countermeasures, various motors, various generators, etc., and a magnetic core using the same And magnetic parts.

Magnetic materials with high saturation magnetic flux density and excellent AC magnetic properties used in various transformers, reactor / choke coils, noise countermeasure components, laser power supplies, pulse power magnetic components for accelerators, various motors, various generators, etc. Silicon steel, ferrite, amorphous alloy, Fe-based nanocrystalline alloy material, and the like are known.
A silicon steel sheet is inexpensive and has a high magnetic flux density, but has a problem of high magnetic core loss for high frequency applications. Due to the manufacturing method, it is extremely difficult to process as thin as an amorphous ribbon, and since the eddy current loss is large, the loss accompanying this is large and disadvantageous. Ferrite materials have a problem of low saturation magnetic flux density and poor temperature characteristics. Ferrites that are easily magnetically saturated are not suitable for high-power applications with high operating magnetic flux density.

  In addition, the Co-based amorphous alloy has a problem that the saturation magnetic flux density is as low as 1 T or less in a practical material and is thermally unstable. For this reason, when used for high power applications, there is a problem that the parts become large and a magnetic core loss increases due to a change with time. Further, since Co is expensive, there is also a problem of price.

Moreover, the Fe-based amorphous soft magnetic alloy as described in Patent Document 1 has a good squareness characteristic and a low coercive force, and exhibits a very excellent soft magnetic characteristic. However, in the Fe-based amorphous alloy system, the saturation magnetic flux density of 1.68 T is almost the physical upper limit value. In addition, the Fe-based amorphous alloy has a problem that its magnetostriction is large and its characteristics are deteriorated due to stress, and there is a problem that noise is large in applications where currents in an audible frequency band are superimposed. In addition, in conventional Fe-based amorphous soft magnetic alloys, when Fe is significantly replaced with other magnetic elements such as Co and Ni, a slight increase in saturation magnetic flux density is also observed, but the inclusion of these elements from the viewpoint of price. It is desirable to make the amount (% by weight) as small as possible. Because of these problems, a soft magnetic material having nanocrystals as described in Patent Document 2 has been developed and used in various applications.
Also disclosed is a technique of obtaining a amorphous alloy having ultrafine crystals as described in Patent Document 3 as a soft magnetic molded body having a high magnetic permeability and a high saturation magnetic flux density and then heat-treating it to nanocrystallize it.

Japanese Patent Laid-Open No. 5-140703 ((0006) to (0010)) Japanese Patent Laid-Open No. 1-156451 (page 2, upper right column, line 19 to lower right column, line 6) JP 2006-40906 A ((0040) to (0041))

  Magnetic core materials such as transformers and saturable reactors are required to be soft magnetic materials having good squareness and being easily magnetized. That is, a soft magnetic characteristic is required in which the ratio of the magnetic flux density Bm obtained with the maximum applied magnetic field Hm to the apparent residual magnetic flux density Br, Br / Bm, has a high value. Although the Fe-based amorphous ribbon exhibits very useful properties in this respect as well, as described above, the upper limit of the saturation magnetic flux density of the Fe-based amorphous ribbon is about 1.68 T, and a soft magnetic material with a higher magnetic flux density is used. It has been demanded. Silicon steel sheets have high magnetic flux density but poor saturation. Depending on the maximum applied magnetic field, the magnetic flux density Bm may be lower than that of the Fe-based amorphous, and in addition, Br / Bm will be lower. Therefore, an object of the present invention is to provide a soft magnetic ribbon that is easily magnetized in a relatively low magnetic field region of 500 A / m or less and has high squareness.

  The soft magnetic ribbon of the present invention has a matrix structure in which crystal grains having a crystal grain size of 60 nm or less (excluding 0) are dispersed in an amorphous material at a volume fraction of 30% or more, and the matrix It has an amorphous layer on the surface side of the tissue.

  The soft magnetic ribbon may be one in which a crystal layer having a crystal structure is formed on the outermost surface, and the amorphous layer is formed on the inner side of the crystal layer. Moreover, you may have a coarse grain layer which consists of a crystal | crystallization with a larger particle size than the average particle diameter of the said mother phase structure between an amorphous layer and a mother phase structure.

The soft magnetic ribbon of the present invention has a composition formula: Fe _100-xy A _x X _y (where A is at least one element selected from Cu and Au, X is B, Si, S, C, And at least one element selected from P, Al, Ge, Ga, and Be), and is preferably characterized by being represented by 0 <x ≦ 5 and 10 ≦ y ≦ 24 in atomic%. .

Further, the soft magnetic ribbon of the present invention has a ratio of the magnetic flux density B ₈₀ at a magnetic field of 80 A / m to the residual magnetic flux density Br after application of the magnetic field, Br / B ₈₀ of 90% or more. Is good.

  By using the soft magnetic ribbon of the present invention as a magnetic core, a magnetic core having an iron loss of 1.5 W / kg or less at 1.5 T and 50 Hz can be obtained.

  Using these soft magnetic ribbons, magnetic components having excellent soft magnetic properties can be obtained.

  According to the present invention, various transformers, laser power supplies, pulse power magnetic parts for accelerators, various reactors for large currents, choke coils for active filters, smooth choke coils, noise countermeasure parts such as electromagnetic shielding materials, motors, generators High saturation magnetic flux density and low loss soft magnetic ribbons that exhibit particularly low magnetic core loss and high-performance magnetic cores and magnetic parts using the same can be realized. There is something.

  The soft magnetic ribbon of the present invention has a matrix structure in which crystal grains having a crystal grain size of 60 nm or less (not including 0) are dispersed in an amorphous material at a volume fraction of 30% or more, and It has the feature of having an amorphous layer on the surface side. These soft magnetic ribbons are alloy ribbons having a thickness of 100 μm or less cast by roll cooling. The soft magnetic ribbon of the present invention has a crystal structure different from the parent phase (outermost surface crystal layer, amorphous layer, coarse crystal grain layer) in the same ribbon, and thus has not been obtained conventionally. It has been found that a soft magnetic ribbon having characteristics can be realized. Moreover, since it has an amorphous layer, it has the characteristic that it is strong to bending.

  FIGS. 7A and 7B are observations of the cross section of the surface on the roll cooling surface side in the soft magnetic ribbon of the present invention. The soft magnetic ribbon of the present invention has a crystal grain size of 60 nm or less (not including 0) at a depth deeper than 120 nm on the surface side of the ribbon (the surface of the roll cooling surface and the free surface behind it). The crystal grains have a matrix structure D in which a volume fraction of 30% or more is dispersed in an amorphous material, and an amorphous layer B is formed on the surface side of the ribbon. In this soft magnetic ribbon, a crystal layer A having a crystal structure is formed on the outermost surface, and the amorphous layer B is formed on the inner side of the crystal layer A. Further, a coarse crystal grain layer C made of crystals having a grain size larger than the average grain size of the matrix structure may be provided between the amorphous layer B and the matrix structure D. Particularly, those having this coarse crystal grain layer C have magnetic properties with good squareness.

The reason why the amorphous layer appears is estimated below. This alloy system has Fe as a main component and Cu and / or Au (hereinafter referred to as element A) is essential. The element A, which is almost non-solid solution with Fe, aggregates to form nano-order clusters and assists in the nucleation of crystal grains. In the portion away from the surface, the A element is easily dispersed uniformly, and therefore a nanocrystalline matrix structure D is formed. In addition, due to the non-solid solution property, the element A is easily segregated on the outermost surface, and the concentration of the element A is increased, and a crystal structure is formed in the same manner as the matrix. On the other hand, in the interior immediately below the outermost surface, the concentration of the A element is lowered by the amount of the A element taken on the surface side. Therefore, in this region, nucleation of crystal grains does not occur and an amorphous layer is formed. In the soft magnetic ribbon of the present invention, a fine crystal grain layer is deposited by heat treatment, and the concentration of the microcrystal grain nuclei is determined by the distribution of element A as described above. For this reason, nuclei are unlikely to appear near the surface, and an amorphous layer appears to be formed.
Elements such as Nb, Mo, Ta, Zr, etc. that have been used in conventional nanocrystal systems have the effect of suppressing segregation and thermal diffusion of the A element. If too much is included, it is difficult to obtain an amorphous layer near the surface. .

Further, the reason why the coarse crystal grain layer C appears is estimated as follows. Further inside the amorphous layer, the concentration of the A element is not as high as that of the region that forms the matrix structure, and nucleation is also low. The grain size of nanocrystal grains is determined by the balance between the concentration of nuclei and the speed of grain growth. In the region of the matrix structure in which the concentration of the A element is uniform, the difference in structure due to the difference in the heating rate does not appear easily. However, in the C region where the A element is low, if the heating rate is slow, it is sufficient for the thermal diffusion of the A element. Given the time, the number of nuclei decreases. Therefore, the crystal grains are easily coarsened, and the coarse crystal grain layer C is formed. For example, when the rate of temperature increase is increased, the crystal grains of the coarse crystal grain layer C become fine and the average grain size approaches the parent phase. Further, the width of the coarse crystal grain layer C decreases. By controlling the rate of temperature rise, the structure is controlled and magnetic properties suitable for the application can be obtained.
Here, the coarse crystal grain layer C refers to a portion that is 1.5 times or more the average crystal grain size of the matrix structure. Moreover, it is preferable that the average crystal grain size of the coarse crystal grain layer C is not more than twice the average crystal grain size of the parent phase structure.

In order to obtain the effect of reducing eddy current loss, the thickness of the soft magnetic ribbon of the present invention is preferably 100 μm or less, and more preferably 40 μm or less. In the present invention, the matrix structure is similar to a structure that is periodically repeated, and a structure composed of crystal grains and grain boundaries in which the distribution of crystal grain sizes is uniform is referred to as a matrix structure. Yes. In soft magnetic ribbons, the structure near the midpoint of the ribbon thickness is the parent phase.
The crystal grain size is measured by taking an average value of the major axis and the minor axis of the structure observed in the structure photograph taken with an electron microscope. The average particle size is an average value of 30 or more crystal grain sizes.
The volume fraction of crystal grains is determined by the line segment method, that is, assuming an arbitrary straight line in the microstructure, the length of the test line is Lt, the length Lc of the line occupied by the crystal phase is measured, and is occupied by the crystal grains. It is _calculated | required by _calculating | requiring the ratio of the length of the line _LL = _Lc / _Lt * 100. Here, the volume fraction of crystal grains is V _V = L _L.

In the soft magnetic ribbon of the present invention, the ratio of the magnetic flux density B ₈₀ at a magnetic field of 80 A / m to the residual magnetic flux density Br after application of the magnetic field, Br / B ₈₀ is 90% or more by performing heat treatment under specific conditions. BH curve with high squareness can be obtained.

  Moreover, by using the soft magnetic ribbon of the present invention as a magnetic core such as a laminated magnetic core or a wound magnetic core, a magnetic core having an iron loss of 1.5 W / kg or less at 1.5 T and 50 Hz can be obtained. The saturation magnetic flux density is 1.65 T or more. In addition, the soft magnetic ribbon of the present invention has a high magnetic flux density region superior to that of conventional directional silicon steel sheets, particularly in a low magnetic field of 500 A / m or less, and a higher saturation magnetic flux density than that of an Fe-based amorphous material. It is. Since the squareness is improved, the apparent power can be kept low, and the magnetic flux density region is expanded.

The crystal grains in the matrix structure are 30% or more in volume fraction. What dispersed 50% or more, further 60% or more is preferable. Although the average crystal grain size needs to be 60 nm or less, a particularly desirable average crystal grain size is 2 nm to 25 nm, and in this range, particularly low coercive force and magnetic core loss can be obtained.
The fine crystal grains formed in the above-described alloy have a body-centered cubic (bcc) crystal phase mainly composed of Fe, and Si, B, Al, Ge, etc. may be dissolved. Further, a regular lattice may be included. The balance other than the crystalline phase is mainly an amorphous phase, but an alloy consisting essentially of the crystalline phase is also included in the present invention. There may be a face-centered cubic structure phase (fcc phase) partially containing Cu and Au.
Further, when an amorphous phase is present around the crystal grains, the resistivity is increased, the crystal grains are refined by suppressing the crystal grain growth, and more preferable soft magnetic characteristics can be obtained.
When the compound phase does not exist in the above alloy, the magnetic core loss is lower, but the compound phase may be partially included.

The soft magnetic ribbon of the present invention has a composition formula: Fe _100-xy A _x X _y (where A is at least one element selected from Cu and Au, X is B, Si, S, C, And at least one element selected from P, Al, Ge, Ga, and Be), and those represented by 0 <x ≦ 5 and 10 ≦ y ≦ 24 in atomic% are preferable. The reason for limitation will be described below.

The amount of element A (Cu, Au) is 5% or less (excluding 0%). The element A in the alloy composition of the present invention is particularly important. As described above, since element A is almost insoluble in Fe, diffusion occurs due to external or internal factors such as heat treatment, mechanical vibration, electrical shock, and magnetic shock. In particular, when heat treatment is performed that tends to cause temperature distribution or temperature difference between the ribbon surface and the inside, there is a site where diffusion is likely to occur and a site where mutual diffusion is likely to be hindered. Will change. In order to control the magnetic properties, it is effective to control the thickness of the ribbon, the composition, the heat treatment temperature during heat treatment, the heat treatment time, the temperature rise rate, and the temperature drop rate. The shape of can be changed. It is also possible to promote the diffusion of Cu atoms by applying other methods, vibrations, or the like.
If the amount of the A element exceeds 5%, the A elements are aggregated and thermal diffusion hardly occurs. Preferably it is 3% or less. In order to obtain the above effect, the element A is preferably added in an amount of 0.1 atomic% or more, further 0.5 atomic% or more, and further 0.8 atomic% or more. For element A, it is preferable to select Cu in consideration of raw material costs.

X element (B, Si, S, C, P, Al, Ge, Ga, Be) is indispensable for forming the soft magnetic ribbon of the present invention in which A element (Cu, Au) exists in the same ribbon. Element. If it is less than 10 atomic%, the effect of promoting the formation of amorphous is insufficient. On the other hand, if it exceeds 24 atomic%, the soft magnetic characteristics are deteriorated. A preferable range is 12 atom% or more and 20 atom% or less.
In particular, B is an important element for promoting the formation of amorphous and is preferably added. When the concentration of B is 10 ≦ y ≦ 20 atomic%, an amorphous phase can be stably obtained while maintaining a high Fe content.
Further, when Si, S, C, P, Al, Ge, Ga, and Be are added, the temperature at which Fe—B having a large magnetocrystalline anisotropy starts to precipitate increases, so that the heat treatment temperature can be increased. High temperature heat treatment increases the proportion of microcrystalline phase, increases B _S , and improves the squareness of the BH curve. In addition, there is an effect of suppressing deterioration and discoloration of the sample surface. The addition amount of Si, S, C, P, Al, Ge, Ga, and Be is preferably more than 0 atomic% to 7 atomic%. Particularly, Si is preferable since this effect is remarkable.

  A part of Fe may be substituted with at least one element selected from Ni and Co that are dissolved in Fe and A elements together. Soft magnetic ribbons substituted with these elements have a higher ability to form an amorphous phase and can increase the content of element A. Increasing the content of element A promotes refinement of the crystal structure and improves soft magnetic properties. In addition, when Ni and Co are replaced, the saturation magnetic flux density increases. Substituting a large amount of these elements leads to an increase in the price. Therefore, the amount of substitution of Ni is less than 10%, preferably less than 5%, more preferably less than 2%. In the case of Co, less than 10%, preferably Less than 2%, more preferably less than 1% is suitable.

Part of Fe is Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, platinum group elements, Ag, Zn, In, Sn, As, Sb, Sb, Bi, Y, N When substituted with at least one element selected from O, O, and rare earth elements, these elements preferentially enter the amorphous phase that remains after heat treatment together with the A element and metalloid element, so that fine grains with high Fe concentration Helps to generate Therefore, it contributes to the improvement of soft magnetic characteristics. On the other hand, since the substantial magnetic player in the soft magnetic ribbon of the present invention is Fe, it is necessary to keep the content of Fe high. However, the inclusion of these elements having a large atomic weight per unit weight The Fe content will decrease. In particular, when the element to be substituted is Nb or Zr, the substitution amount is less than about 5%, more preferably less than 2%. When the element to be substituted is Ta or Hf, the substitution amount is less than 2.5%, More preferably, it is less than 1.2%. Further, when Mn is replaced, the saturation magnetic flux density is lowered, so that the replacement amount is appropriately less than 5%, more preferably less than 2%.
However, in order to obtain a particularly high saturation magnetic flux density, the total amount of these elements is preferably 1.8 atomic% or less. Moreover, it is more preferable that the total amount is 1.0 atomic% or less.

  A specific production method of the present invention is such that the molten metal having the above composition is rapidly cooled at a cooling rate of 100 ° C./sec or more by a quenching technique such as a single roll method, and crystal grains having an average grain size of 30 nm or less are formed in the amorphous phase. After preparing a Fe-based alloy having a structure in which the volume fraction is dispersed in the amorphous phase with a volume fraction of more than 0% and less than 30%, this is processed and heat-treated near the crystallization temperature, and the average particle size is 60 nm or less. It is obtained by forming a microcrystalline structure.

In the present invention, the method of rapidly cooling the molten metal includes a single roll method, a twin roll method, a rotating liquid prevention method, a gas atomization method, a water atomization method, and the like, and can produce flakes, ribbons, and powders. . Further, it is desirable that the molten metal temperature at the time of rapid cooling of the molten metal is higher by about 50 ° C to 300 ° C than the melting point of the alloy.
The ultra-rapid cooling method such as the single roll method can be performed in the atmosphere or in an atmosphere such as local Ar or nitrogen gas when no active metal is contained, but when active metal is contained, Ar, He, etc. The gas atmosphere in the inert gas, nitrogen gas or reduced pressure, or near the roll surface of the nozzle tip is controlled. In addition, a method of spraying CO ₂ gas on the roll, and manufacturing an alloy ribbon while burning CO gas near the roll surface near the nozzle.
In the case of the single roll method, the peripheral speed of the cooling roll is desirably in the range of about 15 m / s to 50 m / s, and the cooling roll is made of pure copper, Cu—Be, Cu—Cr, Cu—Zr, Cu, which has good heat conduction. A copper alloy such as -Zr-Cr is suitable. When manufacturing in large quantities, when manufacturing a thin strip with a large plate thickness or a wide strip, it is preferable that the cooling roll has a water cooling structure.

The heat treatment can be performed in the air, in a vacuum, or in an inert gas such as Ar or nitrogen helium, but it is particularly preferable to perform in an inert gas. By heat treatment, the volume fraction of crystal grains mainly composed of Fe having a body-centered cubic structure is increased, and the saturation magnetic flux density is increased. Moreover, magnetostriction is also reduced by the heat treatment. The soft magnetic alloy of the present invention can be provided with induced magnetic anisotropy by performing a heat treatment in a magnetic field. The heat treatment in a magnetic field is performed by applying a magnetic field having a strength sufficient to saturate the alloy for at least a part of the heat treatment period. Although it depends on the shape of the alloy magnetic core, generally, a magnetic field of 8 kAm ⁻¹ or more is applied when applied in the width direction of the ribbon (in the case of an annular magnetic core: the height direction of the magnetic core), and in the longitudinal direction (in the case of an annular magnetic core). When applying in the magnetic path direction), a magnetic field of 80 Am ⁻¹ or more is applied. As the magnetic field to be applied, any of direct current, alternating current, and a repetitive pulse magnetic field may be used. A magnetic field is usually applied for 20 minutes or more in a temperature range of 200 ° C. or more. A better uniaxial induction magnetic anisotropy is imparted when the temperature is increased, maintained at a constant temperature and during cooling, so that a more desirable DC or AC hysteresis loop shape is realized. By applying heat treatment in a magnetic field, an alloy exhibiting a DC hysteresis loop with a high squareness ratio or a low squareness ratio can be obtained. When heat treatment in a magnetic field is not applied, the soft magnetic ribbon of the present invention becomes a direct current hysteresis loop having a medium squareness ratio. It is desirable to perform the heat treatment in an inert gas atmosphere having a dew point of −30 ° C. or lower. When the heat treatment is performed in an inert gas atmosphere having a dew point of −60 ° C. or lower, the variation is further reduced and a more preferable result is obtained. . In the heat treatment, it is desirable that the maximum temperature be about 70 ° C. higher than the crystallization temperature.

  By controlling the heating rate during the heat treatment, the width of the layered structure of the crystal phase A, the amorphous layer B, and the coarse crystal grain layer C shown in FIG. 7 can be changed, and a BH curve suitable for the purpose is obtained. be able to. For example, when the rate of temperature rise is 100 ° C. or less, the range of the layered structure is widened and the number of different phases increases, so that a large difference occurs between the magnetization process with low coercivity and the magnetization process with high coercivity, The squareness at is improved. Furthermore, in order to bring out this characteristic remarkably, it is preferable that the average temperature rising rate of 300 ° C. or higher is less than 80 ° C./min.

If necessary, the soft magnetic microcrystalline alloy of the present invention covers the surface of the alloy ribbon with a powder or film of SiO ₂ , MgO, Al ₂ O _3, etc., and is surface-treated by chemical conversion treatment to form an insulating layer. A more preferable result can be obtained when an oxide insulating layer is formed on the surface by an anodic oxidation treatment and a treatment such as insulation between the thin ribbon layers is performed. This is particularly because the effect of eddy currents at high frequencies across the layers is reduced and magnetic core loss at high frequencies is improved. This effect is particularly remarkable when used in a magnetic core having a good surface state and a wide ribbon. Furthermore, impregnation and coating can be performed as necessary when producing a magnetic core from the soft magnetic ribbon of the present invention. The soft magnetic ribbon of the present invention is most effective for high-frequency applications, particularly in applications where a pulsed current flows, but can also be used for applications of sensors and low-frequency magnetic parts. In particular, it can exhibit excellent characteristics in applications where magnetic saturation is a problem, and is particularly suitable for applications in high-power power electronics.
The soft magnetic ribbon of the present invention, which is heat-treated while applying a magnetic field in a direction substantially perpendicular to the direction of magnetization during use, has a lower magnetic core loss than a conventional high saturation magnetic flux density material.

Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.
(Example 1)
The molten alloy heated to 1300 ° C by liquid quenching method is jetted into a single roll of 300mm outer diameter Cu-Be alloy rotating at a peripheral speed of 32m / s, and Fe _bal Cu _1.5 Si ₄ B ₁₄ alloy with a thickness of about 20μm A ribbon was prepared. As a result of X-ray diffraction and transmission electron microscope (TEM) observation, it was confirmed that the structure was a structure in which fine crystals were dispersed in an amorphous phase with a volume fraction of less than 30%.
This alloy ribbon was heat treated. The heat treatment patterns were those having an average rate of temperature increase from 300 ° C. to the maximum temperature of less than 100 ° C./min and about 200 ° C./min, respectively. The holding temperature for both heat treatments was 450 ° C. for 10 minutes, and then allowed to cool to obtain the soft magnetic ribbon of the present invention.
FIG. 1 is a photograph of the structure of the surface of a ribbon in the vicinity of the ribbon surface of a soft magnetic ribbon (1-1) according to the present invention having an average temperature increase rate of 300 ° C. or higher during heat treatment of less than 100 ° C./min. . FIG. 8 shows a schematic diagram thereof. In order from the outermost surface, a coarse crystal grain layer C composed of coarse crystal grains having a crystal grain size approximately twice the average crystal grain diameter of the nanocrystal grain layer A, the amorphous layer B, and the parent phase D, and the parent phase D Consists of structure. In the mother phase, fine crystal grains having an average grain size of about 25 nm were present at 80% or more. When the soft magnetic ribbon (1-1) is subjected to heat treatment, the average temperature rising rate of 300 ° C. or higher is controlled to be less than 100 ° C./min, so that a coarse crystal grain layer is likely to precipitate near the surface. . Further, FIG. 2 shows a structure photograph of a sample of the soft magnetic ribbon (1-2) in which an average temperature rising rate of 300 ° C. or higher during heat treatment is about 200 ° C./min. Moreover, the schematic diagram is shown in FIG. In order from the outermost surface, a nanocrystal grain layer A and an amorphous phase B are observed, and then a coarse crystal grain layer C is slightly observed. Furthermore, the mother phase D is seen on the inner side. Moreover, the region of the amorphous phase is narrower than that of the soft magnetic ribbon (1-1). As described above, the layered structure in the vicinity of the surface can be controlled by controlling the average heating rate of 300 ° C. or higher.
For comparison, the molten alloy heated to 1300 ° C by the liquid quenching method was jetted onto a single roll of 300 mm outer diameter Cu-Be alloy rotating at a peripheral speed of 32 m / s, and the composition formula of about 20 µm: Fe _An alloy ribbon comprising _bal Cu _1.5 Si ₄ B ₁₄ Nb ₅ and Fe _bal Cu _1.0 B ₆ Nb _3.5 was prepared. Although the surfaces of these alloy ribbons were observed in the same manner, the amorphous layer as in the present application was not observed, and as shown in the schematic diagram of FIG. 10, the nanocrystalline alloy had almost the same size as a whole. .

(Example 2)
Soft magnetic ribbon of the present invention in FIG. 3 for (1-1) is the maximum magnetic field B _m shows the BH curve of 80A / m. In addition, a BH curve of a soft magnetic ribbon (1-2) having the same composition and an average temperature rising rate of 300 ° C. or higher of 200 ° C. is indicated by a dotted line. These soft magnetic ribbons are the samples shown in FIGS. The BH curve of the soft magnetic ribbon (1-1) with a slow temperature rise rate has better squareness than the soft magnetic ribbon (1-2) with a fast temperature rise rate, and B _r / B ₈₀ is about 94 %, Which is a high value. Moreover, a large magnetic flux density can be obtained with a low magnetic field. In the soft magnetic ribbon (1-2) having a high rate of temperature increase, the B _r / B ₈₀ exhibiting squareness is about 67%, and it is difficult to saturate in a low magnetic field. The Figure 4 shows the BH curve when two of the above samples, the B _m and 800A / m. B800 is about the same as 1.8T, but there is a big difference in the hysteresis in the BH curve over 1.5T. In the soft magnetic ribbon (1-1) having a slow temperature rise rate during the heat treatment, hysteresis exists up to a magnetic field region of 1.5 A or more and 500 A / m. On the other hand, in the soft magnetic ribbon (1-2) having a high temperature rising rate, the hysteresis is reduced in the magnetic flux density region. In general, hysteresis is a loss and it is desirable that hysteresis be small, but squareness may be important depending on the magnetic field and magnetic flux density regions used. 3 and 4, it can be seen that there is a close relationship between the occurrence of hysteresis in the region of 1.5T or more and the squareness of the minor loop. As described above, the shape of the BH curve can be controlled by controlling the average temperature rising rate of 300 ° C. or higher.

(Example 3)
A Fe _bal Cu _1.35 Si ₂ B ₁₄ alloy ribbon with a thickness of about 18 μm was prepared by liquid quenching. The production conditions of the alloy ribbon were the same as in Example 1. It was confirmed that the obtained alloy ribbon had a structure in which fine crystals were dispersed in an amorphous phase by less than 30% in volume fraction. When this alloy ribbon was heat treated so that the rate of temperature increase at 300 ° C. was less than 100 ° C./min, a soft magnetic ribbon having the same structure as the soft magnetic ribbon (1-1) of Example 1 was obtained. Band (2-1) was obtained. FIG. 5 shows a BH curve of the soft magnetic ribbon (2-1). Soft magnetic ribbon of FIG. 3 (1-1) and becomes similar BH curve, B ₈₀ = 1.7 T and a large B was obtained even squareness, to obtain a B _r / B ₈₀ = 94% and high value.

Example 4
In the same manner as in Example 3, soft magnetic ribbons having the alloy compositions shown in Table 1 were produced. The square ratios B _r / B ₈₀₀₀ and B _r / B ₈₀ of this soft magnetic ribbon are shown. As shown in Table 1, the soft magnetic ribbon of the present invention has an amorphous layer. Also, Nanba4-1～4-15 that slow heating rate of the heat treatment B _r / B ₈₀ is a high value of 90% or more, it can be seen that squareness is good. In addition, there is an opening of about 5 to 20% between B _r / B ₈₀₀₀ and B _r / B ₈₀ , and a difference appears in the squareness when a minor loop is drawn and when a full loop is drawn. When a layer composed of coarse crystal grains approximately twice as large as the average crystal grains of the parent phase is deposited near the surface of the ribbon by texture control, the shape of the BH loop changes and the squareness improves. As shown in Table 1, even when the composition is the same, a large difference appears in the squareness depending on the presence or absence of the coarse crystal grain layer. By using such a phenomenon, it is promising as a switching element utilizing the difference in the magnetic field region.

(Example 5)
Fe _bal Cu _1.5 Si ₄ B ₁₄ alloy ribbon (Table 1: 4-1) and Fe _bal Cu _1.35 Si ₂ B ₁₄ alloy ribbon (Table 1: 4-2) ) Was produced. The production conditions of the alloy ribbon were the same as in Example 1. It was confirmed that the obtained alloy ribbon had a structure in which fine crystals were dispersed in an amorphous phase by less than 30% in volume fraction. When this alloy ribbon was heat-treated so that the average rate of temperature increase at 300 ° C. or higher was less than 100 ° C./min, soft magnetism having a structure similar to that of the soft magnetic ribbon (1-1) of Example 1 was obtained. A ribbon was obtained. When the average heating rate of 300 ° C. or higher is small, the average grain size of the coarse crystal grain layer tends to increase.
FIG. 6 shows the magnetic field dependence P _15/50 and P _{15.5 / 50} of the apparent power in the soft magnetic ribbons (Tables 1: 4-1, 4-2) of the present invention. In addition, data of a soft magnetic ribbon (Table 1: 4-13) having the same composition when the average heating rate of 300 ° C. or higher is 200 ° C./min is also described. For comparison, data on grain-oriented silicon steel sheets and Fe-based amorphous materials are also shown.
Table 2 shows iron losses P _15/50 and P _{15.5 / 50} and apparent powers S _15/50 and S _{15.5 / 50} at 1.5 T and 1.55 T at 50 Hz. In a low magnetic field, the apparent power is larger than that of the Fe-based amorphous material, but the apparent power is lower than that of both the Fe-based amorphous material and the silicon steel plate in the region of about 1.5 T or more and less than 1.7 T. Especially in the soft magnetic ribbon (4-2) of the present invention, P _16/50 = 0.35, P _{16.5 / 50} = 0.41, S _16/50 = 0.42, S _{16.5 / 50} = 0.53 and 1.6 to 1.7 T, The lowest iron loss and apparent power. Further, when the soft magnetic ribbon 4-1 having the coarse crystal grain layer is compared with the soft magnetic ribbon 4-13 having the same composition and no coarse crystal grain layer, the soft magnetic ribbon 4 having the coarse crystal grain layer is compared. In the case of -1, the apparent power is lower in the vicinity of 1.4 to 1.6T. The thin ribbon of the present invention has a saturation magnetic flux density of about 15% higher than that of the Fe-based amorphous material, and the saturation magnetic flux density is 1.8 T or more. In addition, since the saturation is better than that of the silicon steel sheet, a region having an apparent power characteristic superior to that of the silicon steel sheet exists in 1.4T ≦ B, which is promising as a soft magnetic material.

Tables 3-1 and 3-2 show various compositions. The dependence of the magnetic flux density and the squareness ratio B _r / B _{80 on} the heat treatment temperature and the heating rate is shown. The ribbon has a width of about 5 mm and a thickness of about 21 μm. In all the compositions in the table below, the squareness ratio B _r / B ₈₀ is 90% or more.

  By composing magnetic parts from this high saturation magnetic flux density and low loss soft magnetic ribbon, various reactors for large currents such as anode reactors, choke coils for active filters, smooth choke coils, various transformers, magnetic shields, electromagnetic High-performance or small-sized magnetic parts suitable for noise countermeasure parts such as shielding materials, laser power supplies, pulse power magnetic parts for accelerators, motors, generators, and the like can be realized.

The structure | tissue photograph which shows the layered structure seen near the surface of a soft-magnetic ribbon. The structure | tissue photograph which shows another layered structure. BH curve (maximum magnetic field 80A / m) comparing samples with different heat-up rates. B-H curve (maximum magnetic field 800A / m) comparing samples with different heating rates. BH curve of soft magnetic ribbon of Example 3 (maximum magnetic field 80 A / m). The figure which shows the magnetic flux density dependence of the apparent electric power of a soft-magnetic material. The schematic diagram which shows the state of the structure | tissue of the soft-magnetic ribbon of this invention. It is a schematic diagram of the structure | tissue photograph of FIG. It is a schematic diagram of the structure | tissue photograph of FIG. The schematic diagram which shows the state of the structure | tissue of the conventional soft magnetic ribbon.

Explanation of symbols

  1: Soft magnetic ribbon, 2: Surface of ribbon

Claims (7)

Crystal grains having a grain size of 60 nm or less (not including 0) have a matrix structure in which a volume fraction of 30% or more is dispersed in an amorphous material, and an amorphous layer is provided on the surface side of the matrix structure. Soft magnetic ribbon characterized by this. 2. The soft magnetic ribbon according to claim 1, wherein a crystal layer having a crystal structure is formed on an outermost surface of the soft magnetic ribbon, and the amorphous layer is formed on an inner side of the crystal layer. . The soft crystal according to claim 1, wherein a coarse crystal grain layer made of crystals having a grain size larger than an average grain size of the matrix structure is provided between the amorphous layer and the matrix structure. Magnetic ribbon. The soft magnetic ribbon has a composition formula: Fe _100-xy A _x X _y (where A is at least one element selected from Cu and Au, X is B, Si, S, C, P Or at least one element selected from Al, Ge, Ga, and Be), and expressed in terms of atomic% by 0 <x ≦ 5 and 10 ≦ y ≦ 24. The soft magnetic ribbon according to claim 3. 5. The soft magnetism according to claim 1, wherein the ratio of the magnetic flux density B ₈₀ at a magnetic field of 80 A / m to the residual magnetic flux density Br after application of the magnetic field, Br / B _80, is 90% or more. Ribbon. A magnetic core using the soft magnetic ribbon according to claim 1, wherein an iron loss at 1.5 T and 50 Hz is 0.5 W / kg or less. A magnetic component using the soft magnetic ribbon according to claim 1.