Soft magnetic alloys, soft magnetic alloy strips, and magnetic components

Abstract

To provide a soft magnetic alloy having high specific resistance and saturation magnetic flux density and low coercive force by means different from the conventional ones. 【Solution means】Composition formula (Fe (1- α ) X1α ) (1-(a+b+c+d+e+f+g+h)) M a B b P c Si d C e Mn f X2 g O h is a soft magnetic alloy having a main component composed of. X1 is one or more selected from the group consisting of Co and Ni, X2 is one or more selected from the group consisting of Al, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N and rare earth elements, and M is one or more selected from the group consisting of Nb, Hf, Zr, Ta, Ti, Mo, W and V. 0.02 ≦ a ≦ 0.10, 0.02 ≦ b ≦ 0.20, 0 ≦ c ≦ 0.10, 0 ≦ d ≦ 0.15, 0 ≦ e ≦ 0.03, 0

Description

[Technical Field]

[0001] This invention relates to soft magnetic alloys, soft magnetic alloy strips, and magnetic components. [Background technology]

[0002] In recent years, there has been a growing demand for lower power consumption and higher efficiency in electronic, information, and communication equipment. Furthermore, these demands are becoming even stronger as we move towards a low-carbon society. Therefore, power supply circuits in electronic, information, and communication equipment also require reduced energy loss and improved power efficiency.

[0003] Furthermore, the magnetic cores of magnetic elements used in power supply circuits are required to have improved saturation magnetic flux density, reduced core loss (magnetic core loss), and improved permeability. Reducing core loss reduces power energy loss, and improving saturation magnetic flux density and permeability allows for miniaturization of magnetic elements, thereby improving efficiency and saving energy. One way to reduce the core loss of the magnetic core is to increase the resistivity of the magnetic material constituting the core and reduce eddy current loss.

[0004] Patent Document 1 describes the development of a soft magnetic alloy with high resistivity and saturation magnetic flux density, as well as low coercivity, by giving the soft magnetic alloy a specific crystal structure. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 6614300 [Overview of the project] [Problems that the invention aims to solve]

[0006] This invention has been made in view of the above circumstances, and its purpose is to provide a soft magnetic alloy that has high resistivity and saturation magnetic flux density, and low coercivity, by means different from conventional methods. [Means for solving the problem]

[0007] In order to achieve the above object, a soft magnetic alloy according to one aspect of the present invention is Composition formula (Fe (1- α ) X1α ) (1-(a+b+c+d+e+f+g+h)) M a B b P c Si d C e Mn f X2 g O h a soft magnetic alloy having a main component composed of, X1 is one or more selected from the group consisting of Co and Ni, X2 is one or more selected from the group consisting of Al, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N and rare earth elements, M is one or more selected from the group consisting of Nb, Hf, Zr, Ta, Ti, Mo, W and V, 0.02 ≦ a ≦ 0.10, 0.020 ≦ b ≦ 0.20, 0 ≦ c ≦ 0.10, 0 ≦ d ≦ 0.15, 0 ≦ e ≦ 0.03, 0 < f ≦ 0.02, 0 ≦ g ≦ 0.03, 0.0001 ≦ h ≦ 0.012, 0.05 ≦ f / h ≦ 100, and 0 ≦ α ≦ 0.5.

[0008] In this soft magnetic alloy, due to reasons such as the easy segregation of Mn oxide (preferably MnO) on the surface of the alloy, a soft magnetic alloy having a high specific resistance, a low coercive force, and a high saturation magnetic flux density can be realized.

[0009] Preferably, 0.730 ≦ 1-(a + b + c + d + e + f + g + h) ≦ 0.918. In this range, the saturation magnetic flux density is particularly improved.

[0010] α may be 0.

[0011] Preferably, it contains Mn oxide.

[0012] Preferably, it has a region where Mn oxide exists within 100 nm from the surface.

[0013] It may have a nanocrystalline structure. The average crystallite diameter of the nanocrystals may be 50 nm or less.

[0014] The soft magnetic alloy ribbon according to one aspect of the present invention has the soft magnetic alloy described in any of the above. The thickness of the soft magnetic alloy ribbon is not particularly limited, but preferably it is 1 μm or more and 100 μm or less.

[0015] The magnetic component according to one aspect of the present invention has the soft magnetic alloy or soft magnetic alloy ribbon described in any of the above.

Brief Description of Drawings

[0016] [Figure 1A] FIG. 1A is a schematic diagram of a single-roll rapid quenching ribbon apparatus used in the single-roll method according to the present embodiment. [Figure 1B] FIG. 1B is a schematic diagram showing the nozzle opening of the cooling nozzle along the line IB-IB in FIG. 1A. [Figure 2] FIG. 2 is a perspective view showing an example of a magnetic core as a magnetic component according to an embodiment of the present invention. [Figure 3] It is a graph showing the results of chemical bond state analysis by XPS according to an example of the present invention. [Figure 4] It is a graph showing the change in the Mn content ratio with respect to the depth from the surface of the soft magnetic alloy according to an example of the present invention. [Figure 5] It is an example of a chart obtained by X-ray crystal structure analysis. [Figure 6] It is an example of a pattern obtained by profile fitting the chart in FIG. 5.

Mode for Carrying Out the Invention

[0017] The embodiments will be described below.

[0018] (First Embodiment) alloy composition The soft magnetic alloy according to this embodiment is Composition formula (Fe (1- α ) X1α ) (1-(a+b+c+d+e+f+g+h)) M a B b P c Si d C e Mn f X2 g O h A soft magnetic alloy having a main component consisting of the following: X1 is one or more selected from the group consisting of Co and Ni. X2 is one or more elements selected from the group consisting of Al, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, and rare earth elements. M is one or more elements selected from the group consisting of Nb, Hf, Zr, Ta, Ti, Mo, W, and V. 0.02 ≤ a ≤ 0.10, 0.02 ≤ b ≤ 0.20, 0 ≤ c ≤ 0.10, 0 ≤ d ≤ 0.15, 0≦e≦0.03, 0 <f≦0.02、 0 ≤ g ≤ 0.03, 0.0001≦h≦0.012, 0.05≦f / h≦100, and 0 ≤ α ≤ 0.5.

[0019] The components of the soft magnetic alloy according to this embodiment will be described in detail below.

[0020] M is one or more elements selected from the group consisting of Nb, Hf, Zr, Ta, Ti, Mo, W, and V.

[0021] The content of M (a) satisfies 0.02 ≤ a ≤ 0.10, preferably 0.04 ≤ a ≤ 0.10, and more preferably 0.05 ≤ a ≤ 0.08. When a is small, the resistivity of the soft magnetic alloy tends to be low, the coercivity tends to be high, and the permeability μ' tends to be low. When a is large, the saturation magnetic flux density of the soft magnetic alloy tends to decrease.

[0022] The content of B (b) satisfies 0.02 ≤ b ≤ 0.20, may be 0.025 ≤ b ≤ 0.20, preferably 0.06 ≤ b ≤ 0.18, and more preferably 0.080 ≤ b ≤ 0.18. When b is small, the resistivity of the soft magnetic alloy tends to be low, the coercivity tends to be high, and the permeability μ' tends to be low. When b is large, the saturation magnetic flux density of the soft magnetic alloy tends to decrease.

[0023] The P content (c) satisfies 0 ≤ c ≤ 0.10, may be 0.001 ≤ c ≤ 0.10, and preferably 0.003 ≤ c ≤ 0.10. By setting P within the above range, the resistivity of the soft magnetic alloy is improved and the coercivity is reduced. If c is too large, the saturation magnetic flux density of the soft magnetic alloy tends to decrease.

[0024] The Si content (d) satisfies 0 ≤ d ≤ 0.15, and preferably 0 ≤ d ≤ 0.10. The presence of Si particularly improves the resistivity of the soft magnetic alloy and reduces its coercivity. Furthermore, the improved resistivity of the soft magnetic alloy allows a high permeability μ' to be maintained even at high frequencies. When d is large, the coercivity of the soft magnetic alloy tends to increase.

[0025] The content ratio (e) of C satisfies 0 ≦ e ≦ 0.03, preferably 0 ≦ e ≦ 0.025, and more preferably 0 ≦ e ≦ 0.02. By containing C, the coercive force of the soft magnetic alloy is particularly likely to decrease, and it becomes easier to maintain a high magnetic permeability μ' up to a high frequency. When e is large, the specific resistance and saturation magnetic flux density of the soft magnetic alloy decrease, and conversely, the coercive force increases. Furthermore, it becomes difficult to maintain a high magnetic permeability μ' up to a high frequency.

[0026] The content ratio (f) of Mn satisfies 0 < f ≦ 0.02, may be 0.0001 ≦ b ≦ 0.02, and is preferably 0.0005 ≦ f ≦ 0.01. When f is 0, the specific resistance of the soft magnetic alloy tends to be low. When f is large, the coercive force increases and the saturation magnetic flux density of the soft magnetic alloy tends to decrease.

[0027] X2 is one or more selected from the group consisting of Al, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, and rare earth elements, and preferably one or more selected from the group consisting of Zn, Sn, Cu, Cr, Bi, La, and Y.

[0028] The content ratio (g) of X2 satisfies 0 ≦ g ≦ 0.03, but X2 may not be contained.

[0029] The content ratio (h) of O satisfies 0.0001 ≦ h ≦ 0.012, may be 0.00011 ≦ h ≦ 0.010, or may be 0.0003 ≦ h ≦ 0.0050. When h is close to 0, the specific resistance of the soft magnetic alloy tends to be low, for example, because Mn on the surface is less likely to exist as MnO. When h is large, the coercive force increases and the saturation magnetic flux density of the soft magnetic alloy tends to decrease.

[0030] The relationship between the content ratio (f) of Mn and the content ratio (h) of O satisfies 0.05 ≦ f / h ≦ 100, may be 0.2 ≦ f / h ≦ 50, or may be 0.5 ≦ f / h ≦ 40.

[0031] X1 is one or more elements selected from the group consisting of Co and Ni. The content (α) of X1 may be α=0, meaning that X1 may not be present at all. In this embodiment, the content (α) of X1 is defined as the proportion of Fe that is substituted, and it is preferable that 0 ≤ α ≤ 0.5 is satisfied.

[0032] (Fe (1- α ) X1α There are no particular restrictions on the content ratio of (1-(a+b+c+d+e+f+g+h)), but it is preferable that 0.730 ≤ (1-(a+b+c+d+e+f+g+h)) ≤ 0.918. By keeping (1-(a+b+c+d+e+f+g+h)) within the above range, it becomes less likely for a crystalline phase consisting of crystals with a particle size larger than 50 nm to form.

[0033] The soft magnetic alloy of this embodiment may contain elements other than those mentioned above as unavoidable impurities. For example, it may contain 0.1% by weight or less of these elements based on 100% by weight of the soft magnetic alloy.

[0034] Manufacturing method The method for manufacturing the soft magnetic alloy according to this embodiment will be described below. First, a thin strip of soft magnetic alloy is manufactured.

[0035] There are no particular limitations on the method for manufacturing the soft magnetic alloy strip in this embodiment. In this embodiment, for example, the soft magnetic alloy strip is manufactured by a single-roll method. The strip may also be a continuous strip.

[0036] In the single-roll method, first, pure raw materials of each element other than oxygen, which will be included in the final soft magnetic alloy thin strip, are prepared and weighed to have the same composition as the elements other than oxygen in the final soft magnetic alloy thin strip. Then, the pure raw materials of each element are melted and mixed to produce the master alloy. The method of melting the pure raw materials is arbitrary, but one method is to melt them in a chamber under vacuum and then heat them with high-frequency induction.

[0037] Next, the prepared master alloy is heated and melted to obtain molten metal. There are no particular restrictions on the temperature of the molten metal, but it can be, for example, 1100 to 1600°C.

[0038] Figure 1A shows a schematic diagram of a single-roll rapid cooling thin strip apparatus used in the single-roll method according to this embodiment. Inside the chamber 35, molten metal 32 is continuously injected as a liquid from the nozzle 31 through a slit at the bottom of the nozzle 31 to the roll 33 which is rotating in the direction of the arrow, thereby rapidly cooling the molten metal 32 and stretching a uniform thin strip 34 in the direction of rotation of the roll 33.

[0039] By spraying water onto this thin strip from a cooling nozzle 36, a water film is created, which rapidly cools the thin strip, yielding a soft magnetic alloy thin strip.

[0040] In this embodiment, the material of the roll 33 is, for example, Cu. There are no particular restrictions on the atmosphere inside the chamber 35, but an atmospheric environment is particularly suitable for mass production.

[0041] The shape and dimensions of the injection port 36a of the cooling nozzle 36 are not particularly limited, and various shapes such as circles, ovals, and rectangles can be used in addition to the rectangle shown in Figure 1B, but it is preferable that it has a width or diameter (including the major axis) equal to or greater than the width of the thin strip. It is desirable to cool the thin strip by applying water over its entire width.

[0042] Furthermore, while there are no particular restrictions on the pressure of the injected water, as long as it is sufficient to rapidly cool the thin strip, if the pressure is too high, the thin strip will pulverize and will no longer form a continuous body. For this reason, the water pressure is preferably 100kPa or less, 50kPa or less, or 10kPa or less.

[0043] Furthermore, there are no particular restrictions on the temperature of the water to be sprayed, but it is sufficient to rapidly cool the thin strip, and for example, 10 to 80°C is preferable.

[0044] The thicker the water film, the easier it is to obtain a soft magnetic metal alloy thin strip with a higher Mn concentration at the surface.

[0045] Since the rapidly cooled thin strip will have the sprayed cooling water remaining on its surface, a mechanism to remove this water may be provided. There are no restrictions on this mechanism, but for example, the thin strip and water may be separated by injecting gas from the gas injection mechanism 37 immediately afterward. There are no restrictions on the gas used. Examples include N2 gas and Ar gas.

[0046] The soft magnetic alloy strip 34 obtained by the above method may contain crystals with a particle size larger than 50 nm, but preferably does not. The soft magnetic alloy strip 34 may have a structure consisting only of amorphous material, or crystals with a particle size of 50 nm or less may be present in the amorphous material (for example, a nanoheterostructure). Coercivity tends to increase as the crystal size increases. The soft magnetic alloy strip 34 may contain initial microcrystals. Here, initial microcrystals refer to crystals contained in the alloy before nanocrystallization treatment. The initial microcrystals preferably have an average particle size of 0.3 to 10 nm.

[0047] There are no particular restrictions on the method for determining whether or not the soft magnetic alloy thin strip 34 contains crystals with a particle size larger than 50 nm. For example, the presence or absence of crystals with a particle size larger than 50 nm can be confirmed by conventional X-ray diffraction measurements. Alternatively, it may be directly observed using a transmission electron microscope.

[0048] Furthermore, there are no particular restrictions on the method for observing the presence or absence of microcrystals and the average particle size. For example, this can be confirmed by obtaining a limited-field diffraction pattern, nanobeam diffraction pattern, bright-field image, or high-resolution image using a transmission electron microscope on a sample thinned by ion milling. When using a limited-field diffraction pattern or nanobeam diffraction pattern, ring-shaped diffraction is formed in the diffraction pattern if the material is amorphous, while diffraction spots due to the crystalline structure are formed if the material is not amorphous. When using a bright-field image or high-resolution image, the magnification should be 1.00 × 10⁻⁶. 5~3.00 x 10 5 By observing the sample visually at double magnification, the presence or absence of microcrystals and the average particle size can be observed.

[0049] When using X-ray diffraction measurement, the amorphousness rate X is calculated using the following formula (1), and if the amorphousness rate X is 85% or higher, it can be determined that the material is amorphous.

[0050] X=100―(Ic / (Ic+Ia)×100)...(1) Ic: Crystalline scattering integrated intensity Ia: Amorphous scattering integrated intensity

[0051] The amorphous fraction X is calculated by performing X-ray crystal structure analysis on soft magnetic metal powder using XRD to identify the phase, reading the peaks of crystallized Fe or compound (Ic: crystalline scattering integral intensity, Ia: amorphous scattering integral intensity), determining the crystallization fraction from the peak intensity, and calculating it according to (1) above. The calculation method will be explained in more detail below.

[0052] X-ray crystal structure analysis is performed on a thin strip of soft magnetic metal alloy according to this embodiment by XRD to obtain a chart as shown in Figure 5. Profile fitting is performed using the Lorentz function described in (2) below to obtain a crystalline component pattern αc showing crystalline scattering integral intensity, an amorphous component pattern αa showing amorphous scattering integral intensity, and a combined pattern αc + a as shown in Figure 6. The amorphous fraction X is determined from the crystalline scattering integral intensity and amorphous scattering integral intensity of the obtained patterns by (1) above. The measurement range is set to a diffraction angle 2θ = 30° to 60° where a halo originating from amorphous material can be observed. Within this range, the error between the integral intensity measured by XRD and the integral intensity calculated using the Lorentz function should be within 1%.

[0053]

number

[0054] In the case of amorphous materials, whether or not they contain initial microcrystals can be determined by measurement using a transmission electron microscope. If the amorphous ratio X is less than 85% and the average crystal grain size is 50 nm or less, it can be determined that the material consists of nanocrystals. If the amorphous ratio X is less than 85% and the average crystal grain size is greater than 50 nm, it can be determined that the material consists of crystals.

[0055] In this embodiment, the alloy strip is subsequently subjected to a crystallization heat treatment to precipitate nanocrystals, particularly Fe-based nanocrystals, but this crystallization heat treatment is not necessarily required. Fe-based nanocrystals are crystals with a particle size on the nanoscale and a bcc (body-centered cubic lattice) crystal structure of Fe. In this embodiment, Fe-based nanocrystals with an average particle size of 5 to 50 nm may be precipitated. Soft magnetic alloys with such Fe-based nanocrystals precipitated tend to have a high saturation magnetic flux density and a low coercivity.

[0056] The heat treatment conditions for precipitating nanocrystals, particularly Fe-based nanocrystals, are not particularly limited as long as the oxidation of the surface of the soft magnetic alloy strip 34 does not proceed excessively. For example, the heat treatment atmosphere is preferably an inert atmosphere such as in Ar gas, or a vacuum atmosphere, in order to maintain the surface state of the soft magnetic alloy. The preferred heat treatment temperature conditions vary depending on the composition of the soft magnetic alloy strip 34. Typically, the preferred heat treatment temperature (crystallization heat treatment temperature) is approximately 400 to 700°C, and the preferred heat treatment time is approximately 0.5 to 10 hours. However, depending on the composition, there may be preferred heat treatment temperatures and times outside of the above ranges.

[0057] By performing heat treatment in an inert atmosphere or a vacuum atmosphere, Fe-based nanocrystals are deposited while maintaining the surface condition. By depositing Fe-based nanocrystals, soft magnetic alloy thin strips with good soft magnetic properties can be easily obtained.

[0058] The thickness of the soft magnetic alloy strip in this embodiment is not particularly limited, but may be in the range of 1 to 100 μm, for example. Furthermore, it is preferable that the soft magnetic alloy strip in this embodiment has a region in which Mn oxide (preferably MnO) exists within 100 nm from its surface. Whether or not Mn oxide is present within 100 nm from the surface can be determined, for example, by performing chemical bonding state analysis and compositional analysis on the surface of the strip using XPS. After that, the strip can be etched in the thickness direction from the surface, and the depth of the MnO-containing region from the surface of the strip can be measured by performing XPS analysis again. The compositional analysis of the strip surface may be performed on one side or both sides of the strip. In addition, ICP analysis or oxygen-nitrogen analysis may be used for compositional analysis, or SEM-EDS or EPMA may be used for analysis.

[0059] For example, Figure 3 shows the results of chemical bonding state analysis by XPS. As shown in Figure 3, a peak for MnO is observed. Subsequently, by repeatedly performing compositional analysis in the thickness direction to a predetermined depth, the depth (width) of the MnO-existing region can be measured. In this case, the depth at which the Mn concentration remains at 0.3 at% or higher from the surface can be determined as the MnO-existing region. For example, as shown in Figure 4, when the Mn concentration exceeds a predetermined value (arrow position) from the surface, it becomes less than 0.3 at%, and this boundary can be defined as the depth of the MnO-existing region. The depth of the MnO-existing region is not particularly limited, but it is preferably within 100 nm from the surface, and also preferably within 90 nm, 5 to 100 nm, or 5 to 90 nm.

[0060] In this embodiment, the soft magnetic alloy strip 34 containing amorphous or nanocrystalline material may be crushed in a crushing device. The crushing device is not particularly limited. For example, the crushing device has a pair of crushing rollers, and the circumferential surfaces of the rollers are formed with crushing irregularities. The crushing irregularities can be formed, for example, by knurling the circumferential surfaces of the rollers.

[0061] These rollers rotate in opposite directions to each other, gripping a single or multi-layered soft magnetic alloy strip from both sides, crushing the strip and producing particles that become soft magnetic powder.

[0062] The particles, which are crushed by passing them between rollers, may be further crushed in another grinding device or classified in a classifying device. Examples of other grinding devices include ball mills, faculty mills, and jet mills.

[0063] There are no particular limitations on the applications of the soft magnetic alloy according to the embodiments described above. The soft magnetic alloy according to the embodiments may be used alone or in combination with other soft magnetic alloys. For example, a toroidal magnetic core as shown in Figure 2 may be manufactured by laminating soft magnetic alloy strips, or by molding soft magnetic alloy powder together with resin, or by winding soft magnetic alloy strips. Alternatively, magnetic cores or magnetic components of other shapes may be manufactured in the same manner. Wires may be wound around the magnetic core and used as electronic components such as inductors (especially power devices such as power inductors) and transformers.

[0064] Electronic components such as inductors are incorporated into and used in electronic devices such as mobile phones and personal computers. Examples of magnetic components other than magnetic cores include thin-film inductors, magnetic heads, and magnetic shielding sheets, which are also incorporated into and used in electronic devices. [Examples]

[0065] The present invention will be described below based on more detailed examples, but the present invention is not limited to these examples.

[0066] (Experimental Example 1a) The raw materials were weighed to achieve the alloy composition shown in Table 1, melted using high-frequency heating, and prepared the master alloy. Subsequently, the prepared master alloy was heated and melted, and using the apparatus shown in Figure 1A, for example, the metal was brought to a molten state of 1100-1600°C according to the alloy composition. Then, the metal was sprayed onto roll 33 using a single-roll method in an atmospheric environment to produce thin strips.

[0067] In Experimental Example 1, M was set to Nb. The material of roll 33 was Cu. The nozzle opening of the cooling nozzle was rectangular in shape with a long side W of 75 mm and a short side T of 0.50 mm, as shown in Figure 1B. The water pressure was set to 1 kPa and the water temperature to 20°C. That is, a soft magnetic thin strip was prepared under the conditions described in Table 1A. The width of the thin strip was 50 mm, which is less than or equal to the long side of the nozzle opening of the high-pressure nozzle, and the thickness was 20 μm. Subsequently, the thin strip was subjected to crystallization heat treatment in an Ar atmosphere at 600°C for 60 minutes to obtain the alloy thin strip corresponding to sample number 8. The composition of the obtained alloy thin strip was obtained by ICP analysis, CS analysis, and oxygen analysis.

[0068] For the thin band, X-ray diffraction measurements were performed to calculate the amorphousness ratio X. If the amorphousness ratio X was 85% or higher, it was considered to be amorphous.

[0069] In the case of amorphous materials, the presence or absence of initial microcrystals was determined by measurement using a transmission electron microscope. If the amorphous ratio X was less than 85% and the average crystal grain size was 50 nm or less, it was considered to consist of nanocrystals. If the amorphous ratio X was less than 85% and the average crystal grain size was greater than 50 nm, it was considered to consist of crystals. It was confirmed that the thin band was composed of nanocrystals.

[0070] Subsequently, resistivity, saturation magnetic flux density, and coercivity were measured for the thin strip. Resistivity (ρ) was measured using the four-probe resistivity method. Saturation magnetic flux density (Bs) was measured using a vibrating sample magnetometer (VSM) at a magnetic field of 1000 kA / m. Coercivity (Hc) was measured using a DC BH tracer at a magnetic field of 5 kA / m. The results are shown in Table 1.

[0071] Table 1 indicates that a resistivity of 75.0 μΩcm or higher was considered good. A saturation magnetic flux density of 1.50 T or higher was considered good. A coercivity of 10 A / m or less was considered good.

[0072] In the examples shown below, unless otherwise specified, all samples were confirmed to have Fe-based nanocrystals with an average particle size of 5-50 nm and a bcc crystal structure through X-ray diffraction measurements and observation using a transmission electron microscope.

[0073] Furthermore, chemical bonding state analysis was performed on the surface of the thin strip using XPS. Figure 3 shows the results of the chemical bonding state analysis by XPS. As shown in Figure 3, a peak for MnO was observed. Subsequently, the thin strip was etched from the surface in the thickness direction, and compositional analysis was performed again by XPS. Compositional analysis was repeated in the thickness direction up to 75 nm.

[0074] Then, the depth to which the Mn concentration remained above 0.3 at% from the surface was determined as the MnO-existing region. The results are shown in Figure 4 and Table 2. As shown in Table 2 and Figure 4, when the Mn concentration exceeds a predetermined value (arrow position) from the surface, it falls below 0.3 at%, and this boundary was determined as the depth of the MnO-existing region (shown as MnO depth in the table).

[0075] Furthermore, as shown in Table 1, samples 2 to 13 were subjected to similar measurements as sample 6, except that the length T of the short side of the injection hole of the cooling nozzle was varied. The results are shown in Tables 1 and 2.

[0076] (Experimental Example 1b) Thin strip fabrication using the single-roll method: 1.0 × 10 -3 Except for being carried out in a vacuum atmosphere below Pa and not being cooled with cooling water, an alloy strip was prepared in the same manner as for sample number 2, and the strip corresponding to sample number 1 was obtained. The obtained strip was evaluated in the same manner as for experimental example 1.

[0077] The results are shown in Table 1. As shown in Table 1, no MnO peak was observed in the chemical bonding state analysis by XPS, but the presence of Mn was confirmed in the compositional analysis by ICP. Since no MnO peak was observed, the MnO depth was not measured. This is indicated by "-" in the table.

[0078] (Experimental Example 1c) Except for changing the cooling conditions with cooling water to the values ​​listed in Table 1, an alloy strip was prepared in the same manner as for sample number 2, and a strip corresponding to sample number 14 was obtained. The obtained strip was evaluated in the same manner as in experimental example 1. The results are shown in Table 1.

[0079] [Table 1]

[0080] [Table 2]

[0081] Rating 1 Table 1 shows that each example, where the content ratio of each component is within the predetermined range, can achieve both high resistivity, low coercivity, and high saturation magnetic flux density. In contrast, sample number 1, where the content ratio h of O was small, showed low resistivity. Furthermore, in the comparative example with a large content ratio h of O, the coercivity increased while the saturation magnetic flux density decreased.

[0082] For the thin strips of sample numbers 1 and 2, it was found that Mn did not exist as an oxide, but rather as elemental Mn, at least on the surface. Furthermore, it was observed that the depth of MnO tended to increase as the O content h increased.

[0083] Experimental Example 2a Alloy strips for samples 15-21 were prepared in the same manner as for sample 4, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the length of the short side of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 4. The results are shown in Table 3.

[0084] Experimental Example 2b Alloy strips for samples 22-28 were prepared in the same manner as for sample 5, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the short side length of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 5. The results are shown in Table 3.

[0085] Experimental Example 2c Alloy strips for samples 29-35 were prepared in the same manner as for sample 6, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the short side length of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 6. The results are shown in Table 3.

[0086] Experimental Example 2d Alloy strips for samples 36-42 were prepared in the same manner as for sample 8, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the short side length of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 8. The results are shown in Table 3.

[0087] Experimental Example 2e Alloy strips for samples 43-48 were prepared in the same manner as for sample 19, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the short side length of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 19. The results are shown in Table 3.

[0088] Experimental Example 2f Alloy strips for samples 49-54 were prepared in the same manner as for sample 13, except that the Mn content f was varied and the MnO depth was adjusted by adjusting the short side length of the cooling nozzle, so that the Mn and O content ratios matched the values ​​shown in Table 3. The obtained strips were evaluated in the same manner as for sample 13. The results are shown in Table 3.

[0089] [Table 3]

[0090] Rating 2 As shown in Table 3, even when f and h are varied, each example in which the content ratio of each component satisfies the predetermined configuration can achieve both high resistivity, low coercivity, and high saturation magnetic flux density. Furthermore, it was found that a MnO depth of 100 nm or less or 40 nm or less is preferable.

[0091] Experimental Example 3a Alloy strips were prepared in the same manner as for sample number 8, except that each component was adjusted to the composition shown in Table 4A, and evaluated in the same way as for sample number 8. The results are shown in Table 4A.

[0092] [Table 4A]

[0093] Rating 3a The results in Table 4A show that even when the Fe content is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration.

[0094] Experimental Example 3b Except for adjusting the content ratio a of component M (Nb) to the value shown in Table 4B, alloy strips were prepared in the same manner as for sample number 6, and evaluated in the same way as for sample number 6. The results are shown in Table 4B.

[0095] [Table 4B]

[0096] Rating 3b The results in Table 4B show that even when the content ratio a of the M component (Nb) is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration. On the other hand, in comparative examples where the content ratio a of the M component (Nb) was small, the coercivity increased. In comparative examples where a was large, the saturation magnetic flux density Bs decreased. Furthermore, there was a tendency for coercivity to increase.

[0097] Experimental Example 4 Except for adjusting the value of the B content b to the value shown in Table 5, a soft magnetic alloy was prepared in the same manner as sample number 8, and evaluated in the same way as sample number 8. The results are shown in Table 5.

[0098] [Table 5]

[0099] Rating 4 The results in Table 5 show that even when the value of b is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration. In the comparative example with a small value of b, the coercivity increased. In the comparative example with a large value of b, the saturation magnetic flux density Bs decreased. Furthermore, the coercivity tended to increase.

[0100] Experimental Example 5 Except for adjusting the value of the P content c to the value shown in Table 6, a soft magnetic alloy was prepared in the same manner as for sample number 8, and evaluated in the same way as for sample number 8. The results are shown in Table 6.

[0101] [Table 6]

[0102] Rating 5 The results in Table 6 show that even when the P content c is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be simultaneously achieved by satisfying the predetermined configuration. In the comparative example with a large P content c, the saturation magnetic flux density Bs decreased. Also, the coercivity tended to increase.

[0103] Experimental Example 6 A soft magnetic alloy was prepared in the same manner as sample number 8, except that the Si content ratio d was adjusted to the value shown in Table 7, and the same evaluation was performed as for sample number 8. The results are shown in Table 7.

[0104] [Table 7]

[0105] Rating 6 The results in Table 7 show that even when the Si content d is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration. In the comparative example with a large Si content d, the saturation magnetic flux density Bs decreased. Also, the coercivity tended to increase.

[0106] Experimental Example 7 Except for adjusting the value of the C content e to the value shown in Table 8, a soft magnetic alloy was prepared in the same manner as sample number 8, and evaluated in the same way as sample number 8. The results are shown in Table 8.

[0107] [Table 8]

[0108] Rating 7 The results in Table 8 show that even when the value of the C content e is varied, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration. In the comparative example with a large C content e, the saturation magnetic flux density Bs decreased. Also, the coercivity tended to increase.

[0109] Experimental Example 8a Except for changing the type of M from Nb to the elements listed in Table 9, alloy strips for samples 93-102 were prepared in the same manner as for sample 63, and evaluated in the same way as for sample 63. The results are shown in Table 9.

[0110] Experimental Example 8b Except for changing the type of M from Nb to the elements listed in Table 9, alloy strips for samples 103-112 were prepared in the same manner as for sample 8, and evaluated in the same way as for sample 8. The results are shown in Table 9.

[0111] Experimental Example 8c Except for changing the type of M from Nb to the elements listed in Table 9, alloy strips for samples 113-122 were prepared in the same manner as for sample 65, and evaluated in the same way as for sample 65. The results are shown in Table 9.

[0112] [Table 9]

[0113] Rating 8 The results shown in Table 9 indicate that even when the type of M is different, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration.

[0114] Experimental Example 9a Except for further weighing of Co and / or Ni as X1 in the proportions listed in Table 10A, alloy strips were prepared in the same manner as for sample number 8, and evaluated in the same manner as for sample number 8. The results are shown in Table 10A.

[0115] Experimental Example 9b Except for further weighing of X2 according to the types and proportions listed in Tables 10B and 10C, alloy strips were prepared in the same manner as for sample number 8, as described in Tables 10B and 10C, and evaluated in the same manner as for sample number 8. The results are shown in Tables 10B and 10C.

[0116] Experimental Example 9c Except for further weighing of X1 and X2 according to the types and proportions listed in Tables 10D and 10E, alloy strips were prepared in the same manner as for sample number 8, as described in Tables 10D and 10E, and evaluated in the same manner as for sample number 8. The results are shown in Tables 10D and 10E.

[0117] [Table 10A]

[0118] [Table 10B]

[0119] [Table 10C]

[0120] [Table 10D]

[0121] [Table 10E]

[0122] Rating 9 The results shown in Tables 10A to E indicate that even when X1 and X2 are within a predetermined range, high resistivity, low coercivity, and high saturation magnetic flux density can be simultaneously achieved by satisfying the predetermined configuration. On the other hand, in the thin band of the comparative example with a large α, the saturation magnetic flux density Bs was lower. In the thin band of the comparative example with a large g, the saturation magnetic flux density Bs was lower. Furthermore, the coercivity tended to increase.

[0123] Experimental Example 10 As shown in Table 11, alloy strips were prepared in the same manner as for sample number 8, except that the crystallization heat treatment conditions were changed, and evaluated in the same manner as for sample number 8. The results are shown in Table 11.

[0124] Furthermore, the average crystallite size was determined for the alloy thin strips corresponding to each sample number shown in Table 11 by X-ray diffraction measurement. The results are shown in Table 11.

[0125] [Table 11]

[0126] Rating 10 The results shown in Table 11 indicate that even when the average crystallite size differs, high resistivity, low coercivity, and high saturation magnetic flux density can be simultaneously achieved by satisfying the predetermined configuration. Furthermore, it was found that coercivity tends to increase as the average crystallite size increases, and the average crystallite size is preferably 50 nm or less.

[0127] Experimental Example 11 Except for adjusting the thickness of the metal strip by changing the roll rotation speed and the gap between the roll and the nozzle, and adjusting the length T of the short side of the cooling nozzle outlet to match the composition, alloy strips described in Tables 12A and 12B were prepared in the same manner as for sample number 6, and evaluated in the same way as for sample number 6. The results are shown in Tables 12A and 12B.

[0128] [Table 12A]

[0129] [Table 12B]

[0130] Rating 11 The results shown in Tables 12A and 12B indicate that even when the thickness of the thin band differs, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously by satisfying the predetermined configuration.

[0131] Experimental Example 12 Alloy strips for samples 347 and 349 were prepared in the same manner as for sample 63, except that the heat treatment temperature corresponding to the crystal heating treatment was changed to the value shown in Table 13, and evaluated in the same manner as for sample 63. Furthermore, alloy strips for samples 346, 348, and 350 were prepared in the same manner as for samples 347, 349, and 63, except that cooling with cooling water was not performed, and evaluated in the same manner as for sample 63. The results are shown in Table 13.

[0132] [Table 13]

[0133] Rating 12 The results shown in Table 13 indicate that lower preheating temperatures result in amorphous structures or structures where microcrystals are present within the amorphous material. On the other hand, even in cases where the structure is amorphous or where microcrystals are present within the amorphous material, it was found that by satisfying the predetermined configuration, high resistivity, low coercivity, and high saturation magnetic flux density can be achieved simultaneously compared to the comparative example. In particular, it was found that high saturation magnetic flux density can be achieved when the structure consists of nanocrystals. [Explanation of Symbols]

[0134] 31… Nozzle 32… Molten metal 33... Roll 34… Thin band 35… Chamber 36… Cooling nozzle 36a... Injection port 37… Gas injection mechanism

Claims

1. Composition formula (Fe (1- α ) X1α ) (1-(a+b+c+d+e+f+g+h)) M a B b P c Si d C e Mn f X2 g O h a soft magnetic alloy having a main component composed of X1 is one or more selected from the group consisting of Co and Ni. X2 is one or more elements selected from the group consisting of Al, Ag, Zn, Sn, As, Sb, Cu, Cr, Bi, N, and rare earth elements. M is one or more elements selected from the group consisting of Nb, Hf, Zr, Ta, Ti, Mo, W, and V. 0.02 ≤ a ≤ 0.10, 0.02 ≤ b ≤ 0.20, 0 ≤ c ≤ 0.10, 0 ≤ d ≤ 0.15, 0 ≤ e ≤ 0.03, 0 < f ≤ 0.02, 0 ≤ g ≤ 0.03, 0.0001 ≤ h ≤ 0.012, 0.05 ≤ f / h ≤ 100, and ０≦α≦０．５ A soft magnetic alloy.

2. The soft magnetic alloy according to claim 1, wherein 0.730 ≤ 1 - (a + b + c + d + e + f + g + h) ≤ 0.

918.

3. The soft magnetic alloy according to claim 1, comprising Mn oxide.

4. The soft magnetic alloy according to claim 3, having a region in which Mn oxide exists within 100 nm from the surface.

5. The soft magnetic alloy according to claim 1, having a nanocrystalline structure.

6. The soft magnetic alloy according to claim 5, wherein the average crystallite diameter of the nanocrystals is 50 nm or less.

7. A soft magnetic alloy strip having the soft magnetic alloy described in any one of claims 1 to 6.

8. The soft magnetic alloy strip according to claim 7, wherein the thickness is 1 μm or more and 100 μm or less.

9. A magnetic component having a soft magnetic alloy according to any one of claims 1 to 6.

10. A magnetic component having a soft magnetic alloy strip as described in claim 7.

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