Fe-based amorphous alloys and Fe-based amorphous alloy ribbons

Abstract

The purpose of the present invention is to provide: an Fe-based amorphous alloy which has low iron loss, high saturation magnetic flux density, and excellent soft magnetic characteristics; and an Fe-based amorphous alloy thin strip. An Fe-based amorphous alloy having excellent soft magnetic characteristics according to the present invention is characterized by containing, in terms of at%, 8.0-18.0% of B, 2.0-9.0% of Si, 0.10-5.00% of C, 0.005-1.50% of Al, 0-1.00% (exclusive of 1.00) of P, 0-0.30% of Mn, and 78.00-86.00% of Fe, with the remainder consisting of impurities, wherein the structure of the Fe-based amorphous alloy is amorphous.

Description

[Technical Field]

[0001] The present invention relates to an Fe-based amorphous alloy having excellent soft magnetic properties and an Fe-based amorphous alloy ribbon having excellent soft magnetic properties. [Background technology]

[0002] Known methods for continuously producing ribbons or wires by rapidly cooling an alloy from a molten state include the centrifugal quenching method, the single-roll method, and the twin-roll method. These methods produce ribbons or wires by ejecting molten metal from an orifice or other opening onto the inner or outer peripheral surface of a metal drum rotating at high speed, causing the molten metal to rapidly solidify. Furthermore, by appropriately selecting the alloy composition, it is possible to obtain amorphous alloys similar to liquid metals, and to produce materials with excellent magnetic or mechanical properties.

[0003] Among amorphous alloys, Fe-based amorphous alloys are particularly promising for use in the iron cores of power transformers and high-frequency transformers. To improve the performance of these applications, there is a strong demand for Fe-based amorphous alloys with low iron loss and high magnetic flux density.

[0004] In Patent Document 1, the composition is TM a Si b B c C d M e (TM is at least one of Fe, Co, and Ni; M is at least one of Al, Ti, and Zr; a to e are atomic %, a: 70 to 85, b: 4 to 18, c: 7 to 18, d: 0 to 4, e: 0.01 to 0.3, and a+b+c+d+e=100), and the amorphous alloy ribbon has excellent magnetic properties and is characterized by having at least one crystallized layer inside the thickness of the alloy, which is produced by ejecting a molten metal of the alloy through a multiple slit nozzle having a plurality of openings onto a moving cooling substrate and rapidly solidifying it.

[0005] Patent Document 2 describes an Fe-based amorphous alloy with excellent soft magnetic properties, which contains, in atomic %, 80.0% to 88.0% Fe, 6.0% to 12.0% B, 2.0% to 8.0% C, 0.10% to 3.0% Si, 0.10% to 2.0% Al, and 0.10% to 6.0% Mo, with the remainder being unavoidable impurities.

[0006] Patent Document 3 describes a compound of the formula: Fe a B b P c Si d C e X f (where X is one or more selected from Al, Sn, Ge, Ti, Zr, Nb, V, Mo, and W; b is 1 to 5 atomic % of B; C is 1 to 10 atomic % of P; d is 4 to 14 atomic % of Si; e is 5 atomic % or less of C; f is 5 atomic % or less of X; and a is (100-(b+c+d+e+f)) atomic % of Fe.)

[0007] Patent Document 4 describes Fe 100-x-y-z Si x B y P z (atomic %) as the main component, where x, y, and z satisfy 0.5≦x≦15, 5≦y≦25, z≦15, and 18≦x+y+z≦30, respectively, and the alloy contains, with respect to the main component, 0.01% by mass to 0.3% by mass of Mn, 0.0001% by mass to 0.01% by mass of Al, 0.001% by mass to 0.03% by mass of Ti, 0.005% by mass to 0.2% by mass of Cu, and 0.001% by mass to 0.05% by mass of S.

[0008] Patent Document 5 describes an Fe-based amorphous alloy ribbon that is obtained by ejecting molten metal onto a moving cooling substrate through a pouring nozzle having a slot-shaped opening, followed by rapid solidification, and that has an extremely thin oxide layer having a thickness of 5 nm to 20 nm on at least one ribbon surface of an amorphous parent phase containing 0.2 atomic % to 12 atomic % of P.

[0009] Although the various ribbons or alloys described in Patent Documents 1 to 5 have certain soft magnetic properties, there is room for further improvement in the soft magnetic properties. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 4-362162 [Patent Document 2] Japanese Patent Application Publication No. 2017-78186 [Patent Document 3] Japanese Patent Application Publication No. 57-185957 [Patent Document 4] Japanese Patent Application Laid-Open No. 2009-174034 [Patent Document 5] International Publication No. 2003 / 085150 Summary of the Invention [Problem to be solved by the invention]

[0011] Fe-based amorphous alloys are considered promising for use in iron cores of power transformers, high-frequency transformers, etc., and for improving the performance of these applications, there is a strong demand for Fe-based amorphous alloys with low iron loss and high magnetic flux density. An object of the present invention is to provide an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that have low iron loss, high saturation magnetic flux density, and excellent soft magnetic properties. [Means for solving the problem]

[0012] In order to solve the above problems, the present invention employs the following configuration.

[0013] [1] An Fe-based amorphous alloy characterized by containing, in atomic %, B: 8.0% to 18.0%, Si: 2.0% to 9.0%, C: 0.10% to 5.00%, Al: 0.005% to 1.50%, P: 0% to less than 1.00%, Mn: 0% to 0.30%, Fe: 78.00% to 86.00%, and the remainder: impurities, and having an amorphous structure.

[0014] [2] The Fe-based amorphous alloy according to [1], characterized in that, in atomic %, the B content is 10.0% or more and 18.0% or less, the Si content is 2.0% or more and 6.0% or less, the C content is 0.10% or more and less than 3.00%, and the P content is 0% or more and 0.05% or less.

[0015] [3] The Fe-based amorphous alloy according to [1], characterized in that, in atomic %, the B content is 11.0% or more and 16.0% or less, the Si content is 2.0% or more and 4.0% or less, the C content is 0.10% or more and less than 3.00%, and the P content is 0% or more and 0.05% or less.

[0016] [4] The Fe-based amorphous alloy according to [1], characterized in that, in atomic %, the B content is 8.0% or more and 16.0% or less, the Si content is more than 2.0% and 9.0% or less, the Al content is 0.005% or more and 1.00% or less, the P content is 0.01% or more and less than 1.00%, and the sum of the P and Al contents is 0.10% or more and 1.50% or less.

[0017] [5] The Fe-based amorphous alloy according to [1], characterized in that, in atomic %, the B content is 8.0% or more and 15.0% or less, the Si content is more than 3.0% and 7.5% or less, the C content is 0.50% or more and 5.00% or less, the Al content is 0.01% or more and 0.80% or less, the P content is 0.01% or more and 0.80% or less, the Fe content is 78.00% or more and 85.00% or less, and the sum of the P and Al contents is 0.10% or more and 1.50% or less.

[0018] [6] The Fe-based amorphous alloy according to [1], characterized in that, in atomic %, the B content is 10.0% or more and 16.0% or less, the Si content is more than 2.0% and 6.0% or less, the C content is 0.10% or more and less than 3.00%, the Al content is 0.01% or more and 1.00% or less, the P content is 0.01% or more and less than 1.00%, the Fe content is 78.00% or more and 84.00% or less, and the sum of the P and Al contents is 0.10% or more and 1.50% or less.

[0019] [7] The Fe-based amorphous alloy according to any one of [1] to [6], characterized in that the Fe is substituted with at least one of Ni, Cr and Co in an amount of 10.0 atomic % or less.

[0020] [8] An Fe-based amorphous alloy ribbon made of the Fe-based amorphous alloy according to any one of [1] to [7]. [Effects of the Invention]

[0021] According to the present invention, it is possible to provide an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that have low iron loss, high saturation magnetic flux density, and excellent soft magnetic properties. DETAILED DESCRIPTION OF THE INVENTION

[0022] Among the various alloy components proposed so far, the present inventors focused on a component system mainly composed of Fe, B, C, and Si, and conducted studies and experiments to achieve low iron loss while maintaining high magnetic flux density. They then focused on Al, which had previously been considered unfavorable for amorphization. As is clear from the fact that Al is used as an element that forms a crystalline phase on the ribbon surface in Patent Document 1, it has long been known as an element that easily forms a crystalline phase. Meanwhile, as described in Patent Document 2, it has also been found that adding Al and Si improves the thermal stability of the amorphous phase.

[0023] Therefore, the inventors conducted detailed experiments on a component system mainly composed of Fe and mainly containing B, C, and Si as added elements, and found that adding a small amount of Al can reduce iron loss. Furthermore, to compensate for the decrease in amorphous layer forming ability due to the addition of Al, the inventors found the optimum content ranges for Si, C, and B. As a result, it is possible to make the saturation magnetic flux density 1.60 T or more, preferably 1.62 T or more, and to reduce iron loss (iron loss W) at a magnetic flux density of 1.3 T and a frequency of 50 Hz without the need for the addition of Mo as described in Patent Document 2. 13 / 50 ) can be reduced to 0.095 W / kg or less, preferably 0.090 W / kg or less, and the inventors have completed an invention relating to an Fe-based amorphous alloy that simultaneously exhibits high saturation magnetic flux density and low core loss.

[0024] Hereinafter, an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon having excellent soft magnetic properties according to this embodiment will be described. In this embodiment, excellent soft magnetic properties refer to low iron loss and high saturation magnetic flux density. Hereinafter, "%" representing the content of an element means "atomic %" unless otherwise specified.

[0025] The Fe-based amorphous alloy of this embodiment contains 8.0% to 18.0% of B, 2.0% to 9.0% of Si, 0.10% to 5.00% of C, 0.005% to 1.50% of Al, 0% to less than 1.00% of P, 0% to 0.30% of Mn, and 78.00% to 86.00% of Fe, with the remainder being impurities that may be present in a total amount of 0.1% or less.

[0026] The Fe-based amorphous alloy of the present embodiment may contain 10.0% or more and 18.0% or less of B, 2.0% or more and 6.0% or less of Si, 0.10% or more and less than 3.0% of C, 0.005% or more and 1.50% or less of Al, 0% or more and 0.05% or less of P, 0% or more and 0.30% or less of Mn, and 78.00% or more and 86.00% or less of Fe.

[0027] The Fe-based amorphous alloy of the present embodiment may contain 11.0% or more and 16.0% or less of B, 2.0% or more and 4.0% or less of Si, 0.10% or more and less than 3.0% of C, 0.005% or more and 1.50% or less of Al, 0% or more and 0.050% or less of P, 0% or more and 0.30% or less of Mn, and 78.00% or more and 86.00% or less of Fe.

[0028] In order to improve workability, the above-mentioned Fe-based amorphous alloy may contain 8.0% or more and 16.0% or less of B, more than 2.0% and 9.0% or less of Si, 0.10% or more and 5.00% or less of C, 0.005% or more and 1.00% or less of Al, 0.01% or more and less than 1.00% of P, and 78.0% or more and 86.0% or less of Fe, with the sum of the P and Al contents being 0.10% or more and 1.50% or less.

[0029] The Fe-based amorphous alloy of this embodiment with improved workability may contain 8.0% or more and 15.0% or less of B, more than 3.0% and 7.5% or less of Si, 0.50% or more and 5.00% or less of C, 0.01% or more and 0.80% or less of Al, 0.01% or more and 0.80% or less of P, 0% or more and 0.30% or less of Mn, and 78.0% or more and 85.0% or less of Fe, with the sum of the contents of P and Al being 0.10% or more and 1.50% or less.

[0030] The Fe-based amorphous alloy of this embodiment with improved workability may contain 10.0% or more and 16.0% or less of B, more than 2.0% and 6.0% or less of Si, 0.10% or more and less than 3.00% of C, 0.01% or more and 1.00% or less of Al, 0.01% or more and less than 1.00% of P, 0% or more and 0.30% or less of Mn, and 78.00% or more and 84.00% or less of Fe.

[0031] In this embodiment, "excellent workability" means that the ribbon made of an Fe-based amorphous alloy has good tear brittleness. "Good tear brittleness" means that the number of brittle spots generated when a certain length of the Fe-based amorphous alloy ribbon is torn in the casting direction is small. The brittle spots are areas where damage occurs in the Fe-based amorphous alloy ribbon, such as changes in the tear path, direction, and fragment separation, when the Fe-based amorphous alloy ribbon is torn.

[0032] Furthermore, in the Fe-based amorphous alloy of this embodiment, Fe in the Fe-based amorphous alloy may be substituted with at least one of Ni, Cr, and Co in a range of 10.0% or less. The Fe-based amorphous alloy ribbon of this embodiment is made of the above-mentioned Fe-based amorphous alloy.

[0033] The reasons for limiting the content of each element in the Fe-based amorphous alloy of this embodiment will be described below.

[0034] B is added to the Fe-based amorphous alloy of this embodiment to improve amorphous phase formation and thermal stability of the amorphous phase. By optimizing the content of this element, the decrease in amorphous phase-forming ability associated with the addition of Al can be counteracted, resulting in a stable amorphous phase in the alloy structure, further improving soft magnetic properties. For example, the saturation magnetic flux density can be stably maintained at 1.60 T or higher. If the B content is less than 8.0%, the amorphous phase-forming ability is not improved, and the amorphous alloy cannot be stably obtained in the Fe-based amorphous alloy. This makes it difficult to stably maintain a saturation magnetic flux density of 1.60 T or higher while maintaining a stable core loss of 0.095 W / kg or lower. On the other hand, if the B content exceeds 18.0%, the amorphous phase-forming ability is not improved, and it becomes difficult to stably maintain a saturation magnetic flux density of 1.60 T or higher. Therefore, the B content is limited to a range of 8.0% to 18.0%. The B content may be 9.0% or more, 10.0% or more, 11.0% or more, or 11.5% or more. The B content may be 17.0% or less, 16.0% or less, 15.5% or less, or 15.0% or less.

[0035] Like B, Si and C are added to the Fe-based amorphous alloy of this embodiment to improve the amorphous phase formation and thermal stability of the amorphous phase. Optimizing the contents of these elements counteracts the decrease in amorphous phase formation ability associated with the addition of Al, making it possible to stably form an amorphous phase in the alloy structure, thereby further improving soft magnetic properties. For example, the saturation magnetic flux density can be stably increased to 1.60 T or more.

[0036] If the Si content is less than 2.0% or the C content is less than 0.10%, the amorphous phase forming ability is not improved, and the amorphous alloy cannot be stably obtained in the Fe-based amorphous alloy. As a result, it becomes difficult to stably achieve a saturation magnetic flux density of 1.60 T or more while maintaining a stable iron loss of 0.095 W / kg or less. On the other hand, if the Si content exceeds 9.0% or the C content exceeds 5.0%, the amorphous phase forming ability is not improved, and it becomes difficult to stably achieve a saturation magnetic flux density of 1.60 T or more. Therefore, the Si content is limited to 2.0% to 9.0% and the C content is limited to 0.10% to 5.00%.

[0037] The Si content may be 2.2% or more, 2.5% or more, 2.8% or more, or 3.0% or more, and may be 7.0% or less, 6.0% or less, 4.0% or less, or 3.5% or less.

[0038] The C content may be 0.20% or more, 0.30% or more, 0.40% or more, or 0.50% or more. The C content may also be less than 3.00%, less than 2.50%, less than 2.00%, or less than 1.50%.

[0039] Al is contained in the Fe-based amorphous alloy of this embodiment to achieve low core loss. However, as the Al content increases, the amorphous phase formation ability decreases, making it difficult to stably obtain an amorphous alloy, making it difficult to stably achieve a saturation magnetic flux density of 1.60 T or more. Therefore, the Al content is set to a range of 0.005 to 1.50%. The Al content may be 0.008% or more, 0.010% or more, 0.05% or more, 0.10% or more, or 0.20% or more. Alternatively, the Al content may be 1.40% or less, 1.30% or less, 1.20% or less, 1.00% or less, or 0.80% or less.

[0040] Like Si, C, and B, P is added to improve amorphous phase formation and the thermal stability of the amorphous phase. By optimizing the content of this element, the decrease in amorphous phase formation ability associated with the addition of Al can be countered, resulting in a stable amorphous phase in the alloy structure. It can also be added to improve the workability of the Fe-based amorphous alloy and improve the tear embrittlement when made into an Fe-based amorphous alloy ribbon. Since P is not an essential element, the lower limit of its content is 0. While these effects can be achieved even with trace amounts, to ensure the improvement in workability, it is preferable that the P content be 0.01% or more. On the other hand, if the P content is 1.00% or more, workability may be reduced. Therefore, it is preferable to limit the P content to a range of 0.01% or more but less than 1.00%. The P content may be 0.03% or more, 0.05% or more, 0.10% or more, 0.15% or more, or 0.20% or more. The P content may also be 0.95% or less, 0.90% or less, 0.80% or less, or 0.70% or less.

[0041] Mn may be added because it has the effect of reducing iron loss in Fe-based amorphous alloys. Since it is not an essential element, the lower limit of its content is 0. Although the effect of reducing iron loss can be obtained even with a small amount of Mn, to ensure the effect of reducing iron loss, it is preferable to add 0.10% or more. On the other hand, if the Mn content exceeds 0.30%, the saturation magnetic flux density may decrease. Therefore, the Mn content is set to 0.30% or less. The Mn content may be 0.12% or more, 0.13% or more, 0.14% or more, or 0.15% or more. The Mn content may also be 0.28% or less, 0.25% or less, 0.22% or less, or 0.20% or less.

[0042] Furthermore, from the viewpoint of the balance between iron loss and workability, it is preferable to limit the sum of the P and Al contents to a range of 0.10% or more and 1.50% or less. Although the inclusion of P and Al reduces iron loss, excessive P and Al contents degrade workability and iron loss, so there is an optimal range for the sum of the P and Al contents. The total amount of P and Al may be 0.15% or more, 0.20% or more, 0.30% or more, or 0.40% or more. Furthermore, the total amount of P and Al may be 1.40% or less, 1.35% or less, 1.30% or less, or 1.20% or less.

[0043] In Fe-based amorphous alloys, if the Fe content is 70% or more, a saturation magnetic flux density at a practical level for a general iron core can be obtained, but to obtain a high saturation magnetic flux density of 1.60 T or more, the Fe content must be 78.00% or more. On the other hand, if the Fe content is too high, it becomes difficult to form an amorphous phase, and the good soft magnetic properties (iron loss W) specific to amorphous alloys are lost. 13 / 50 Since it may be difficult to stably obtain a dielectric constant of 0.095 W / kg or less, the contents of other elements are adjusted within the above ranges so that the Fe content is 86.00% or less. The Fe content may be 78.50% or more, 79.00% or more, 79.50% or more, or 80.00% or more. The Fe content may also be 85.50% or less, 85.00% or less, 84.00% or less, or 83.00% or less.

[0044] In the Fe-based amorphous alloy according to this embodiment, in addition to the above elements, the inclusion of impurities in a total amount of 0.1% or less is permitted. If the total amount of impurities is 0.1% or less, it does not affect the solution of the problem of the present invention, which is to obtain an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that are excellent in soft magnetic properties, having low iron loss and high saturation magnetic flux density.

[0045] Impurities include, for example, impurity elements contained in steel materials when steel materials are used as Fe sources. For example, Ti, N, S, O, etc. may be contained as impurities. The approximate amounts of each element contained as an impurity are 0.005% or less for Ti and S, 0.02% or less for N, and 0.05% or less for O. Even if P is not intentionally contained, it may be contained as an impurity at about 0.05% or less. When P is contained as an impurity, it is preferably 0.04% or less, more preferably 0.03% or less, and even more preferably 0.02% or less.

[0046] These impurity amounts are merely guidelines, and as mentioned above, the total amount of impurities is 0.1% or less, and does not affect the solution of the problems of the present invention. The total amount of impurities may be 0.08% or less, 0.06% or less, or 0.05% or less.

[0047] Furthermore, by substituting at least one of Ni, Cr, and Co for Fe in an Fe-based amorphous alloy in a range of 10.0% or less, it is possible to improve soft magnetic properties such as core loss while maintaining a high saturation magnetic flux density. The upper limit on the amount of substitution by these elements is set because exceeding 10.0% reduces the saturation magnetic flux density and increases raw material costs. When Fe is substituted with one or more of Ni, Cr, and Co, the total content of Ni, Cr, and Co and Fe may be in the range of 78.00% to 86.00%. The total content of Ni, Cr, and Co and Fe may be 78.50% or more, 79.00% or more, 79.50% or more, or 80.00% or more. The total content of Ni, Cr, and Co and Fe may be 85.50% or less, 85.00% or less, 84.00% or less, or 83.00% or less.

[0048] The Fe-based amorphous alloy of this embodiment can usually be obtained in the form of a ribbon. This Fe-based amorphous alloy ribbon can be produced by a method of melting an alloy consisting of the components described in the above embodiment, ejecting the molten metal through a slot nozzle or the like onto a cooling plate moving at high speed, and rapidly solidifying the molten metal, such as by a single-roll method or a twin-roll method. The rolls used in these roll methods are made of metal, and the alloy can be rapidly solidified by rotating the rolls at high speed and causing the molten metal to collide with the roll surface or inner surface.

[0049] Single-roll equipment includes centrifugal quenching equipment that uses the inner wall of a drum, equipment that uses an endless belt, and improved versions of these, such as auxiliary rolls and equipment equipped with roll surface temperature control devices, as well as casting equipment that operates under reduced pressure, vacuum, or inert gas.

[0050] In this embodiment, the dimensions of the ribbon, such as thickness and width, are not particularly limited, but the ribbon thickness is preferably 10 μm or more and 100 μm or less, and the ribbon width is preferably 10 mm or more. The Fe-based amorphous alloy ribbon obtained as described above can be used for applications such as iron cores in power transformers and high-frequency transformers.

[0051] The Fe-based amorphous alloy of this embodiment can be in the form of powder in addition to a ribbon. In this case, a method can be employed in which the molten alloy or droplets of the molten alloy are ejected at high speed from a nozzle of a crucible filled with the molten alloy of the above composition onto a rotating roll or a liquid such as cooling water, thereby causing rapid solidification.

[0052] By the above-mentioned method, it is possible to obtain Fe-based amorphous alloy powder having excellent soft magnetic properties.

[0053] The Fe-based soft magnetic alloy powder obtained as described above can be compacted in a mold or the like to form a desired shape, and if necessary, sintered to form an integrated body, and can be used for applications such as power transformers, high-frequency transformers, and coil cores.

[0054] Whether or not the Fe-based amorphous alloy of this embodiment has an amorphous structure can be confirmed by, for example, X-ray diffraction measurement using an X-ray diffractometer with a Co tube. That is, if no clear diffraction peak is obtained in the X-ray diffraction measurement, it can be confirmed that the Fe-based amorphous alloy has an amorphous structure and does not contain a crystalline phase.

[0055] The Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of the present embodiment have excellent soft magnetic properties when the saturation magnetic flux density and iron loss are measured by the method described below, and the saturation magnetic flux density is 1.60 T or more, and the iron loss (iron loss W) at a magnetic flux density of 1.3 T and a frequency of 50 Hz is 1.60 T or more. 13 / 50 ) is 0.095W / kg or less.

[0056] Iron loss is measured using an SST (Single Strip Tester). The iron loss measurement conditions are a magnetic flux density of 1.3 T and a frequency of 50 kHz. Samples for iron loss measurement are collected from six locations along the entire length of one lot of ribbon. The samples for iron loss measurement are ribbon samples cut to a length of 120 mm. These ribbon samples for iron loss measurement are annealed at 360°C for one hour in a magnetic field (magnetic field: 800 A / m, magnetic field applied in the casting direction) before being used for measurement. The atmosphere during annealing is a nitrogen atmosphere. Meanwhile, saturation magnetic flux density is measured using a VSM (Vibrating Sample Magnetometer) device. The samples for the VSM device are thin sections collected from the center of the width of each of the ribbon samples from the six locations mentioned above.

[0057] According to the Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of this embodiment, by containing Al, optimizing the contents of B, Si, and C, and further setting the Fe content to 78.00% or more, the iron loss (iron loss W 13 / 50 ) is 0.095 W / kg or less, the saturation magnetic flux density is 1.60 T or more, and excellent soft magnetic properties can be exhibited, making it suitable for use in the iron cores of power transformers and high-frequency transformers.

[0058] The Fe-based amorphous alloy and the Fe-based amorphous alloy ribbon of this embodiment can further be provided with excellent workability as an additional effect. "Excellent workability" specifically refers to a case where the brittleness code is 4 or less in the tear brittleness evaluation specified in JIS C 2534:2017. A brittleness code of 4 or less means that the number of brittle spots in one test piece is 9 or less.

[0059] According to this additional effect, in the tearing embrittlement evaluation specified in JIS C 2534:2017, the brittleness code is 4 or less, so that even when slitting or cutting is performed during the process of processing the cast Fe-based amorphous alloy ribbon into a final product, the occurrence of cracks can be suppressed, and the yield of product manufacturing can be improved. [Example]

[0060] Examples of the present invention will be described below.

[0061] Example 1 Fe-based amorphous alloy ribbons were produced by melting alloys with the various compositions shown in Table 1 in an argon atmosphere, then quenching and casting them in a single-roll apparatus. The casting atmosphere was air. The single-roll apparatus used consisted of a copper alloy cooling roll with a diameter of 300 mm, a high-frequency power supply for sample melting, and a quartz crucible with a slotted nozzle at its tip. In this experiment, a slotted nozzle with a length of 10 mm and a width of 0.6 mm was used. The peripheral speed of the cooling roll was 24 m / s. The resulting ribbons had a thickness of approximately 20 μm, a width of 10 mm (depending on the length of the slotted nozzle), and a length of approximately 100 m.

[0062] X-ray diffraction measurements were performed on the obtained Fe-based amorphous alloy ribbon to obtain an X-ray diffraction pattern. The X-ray source for the X-ray diffraction measurements was Co-Kα (wavelength λ=1.7902 Å), and the scan range was 2θ=10° to 120°. Whether a crystalline phase had formed in the metal structure was determined from the shape of the X-ray diffraction pattern.

[0063] The saturation magnetic flux density and iron loss of the Fe-based amorphous alloy ribbon were measured using an SST (Single Strip Tester). The iron loss measurement conditions were a magnetic flux density of 1.3 T and a frequency of 50 kHz. The samples for iron loss measurement were all collected from six locations along the entire length of one lot of ribbon. The samples for iron loss measurement were ribbon samples cut to a length of 120 mm. These ribbon samples for iron loss measurement were annealed at 360°C for one hour in a magnetic field (magnetic field: 800 A / m, magnetic field applied in the casting direction) and then used for measurement. The atmosphere during annealing was a nitrogen atmosphere. On the other hand, the samples for the VSM device were all thin sections collected from the width center of the ribbon samples from the above six locations.

[0064] The saturation magnetic flux density and iron loss measurements were taken at six locations and the average values ​​are shown in Table 1.

[0065] [Table 1]

[0066] As shown in Table 1, in all of Inventive Examples 1 to 18, the alloy composition satisfied the range of the present invention, and therefore the saturation magnetic flux density was 1.60 T or more, and the iron loss (iron loss W 13 / 50 ) was 0.095 W / kg or less, enabling high saturation magnetic flux density and low iron loss to be achieved simultaneously.

[0067] On the other hand, in Comparative Examples 1 to 10, the alloy compositions did not satisfy the range of the present invention, and therefore the iron loss (iron loss W 13 / 50 ) exceeded 0.095 W / kg, and in Comparative Example 11, the alloy composition did not satisfy the range of the present invention, so the saturation magnetic flux density was less than 1.60 T.

[0068] That is, in Comparative Example 1, the iron loss (iron loss W 13 / 50 ) exceeded 0.095 W / kg, and the saturation magnetic flux density was less than 1.60 T. In Comparative Example 2, the iron loss (iron loss W 13 / 50) exceeded 0.095W / kg. In Comparative Examples 3 and 4, the B content was outside the range of the present invention, so the iron loss (iron loss W 13 / 50 ) exceeded 0.095W / kg. In Comparative Examples 5 and 6, the Si content was outside the range of the present invention, so the iron loss (iron loss W 13 / 50 ) exceeded 0.095W / kg. In Comparative Examples 7 and 8, the C content was outside the range of the present invention, so the iron loss (iron loss W 13 / 50 ) exceeded 0.095W / kg. In Comparative Examples 9 and 10, the Al content was outside the range of the present invention, so the iron loss (iron loss W 13 / 50 ) exceeded 0.095W / kg. In Comparative Example 11, the Mn content was outside the range of the present invention, and therefore the saturation magnetic flux density was less than 1.60 T.

[0069] In addition, when X-ray diffraction measurement was performed on the Fe-based amorphous alloy ribbons, no clear diffraction peaks were observed in any of the present invention examples 1 to 18 and the comparative examples 1 to 11. Therefore, it cannot be said that a crystalline phase was formed in the metal structure, and the entire structure was an amorphous phase.

[0070] Example 2 For the alloy shown in Inventive Example No. 1 in Table 1, alloys of various compositions in which part of the Fe was replaced with at least one of Ni, Cr, and Co were used to cast ribbons using the same equipment and conditions as in Example 1. Specific compositions of the alloys used are shown in Table 2. As a result, the thickness, width, and length of the obtained ribbons were approximately 20 μm, 10 mm, and approximately 100 m, respectively. The saturation magnetic flux density and iron loss of the obtained ribbons were evaluated. The sample collection method and measurement conditions used for evaluating these properties were the same as in Example 1. The measurement results are shown in Table 2. The presentation methods in Table 2 are the same as those in Table 1.

[0071] [Table 2]

[0072] As is clear from the results of samples No. 19 to No. 25 in Table 2, even if part of the Fe is replaced with at least one of Ni, Cr, and Co in the range of 10.0 atomic % or less, the saturation magnetic flux density is 1.60 T or more, and the iron loss is reduced to W. 13 / 50 It was found that the power could be stably kept below 0.095 W / kg. Furthermore, no clear diffraction peaks were observed in X-ray diffraction measurements of any of the samples, confirming that they were amorphous.

[0073] As explained above, the Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of the present invention contain Al, and the contents of B, Si, and C are optimized, and the Fe content is set to 78.00% or more, thereby achieving low iron loss (iron loss W 13 / 50 ) was 0.095 W / kg or less, and the saturation magnetic flux density was 1.60 T or more, demonstrating excellent soft magnetic properties.

[0074] Example 3 Fe-based amorphous alloy ribbons were produced by melting alloys with the various compositions shown in Table 3 in an argon atmosphere, quenching them in a single-roll apparatus, and casting them. The casting atmosphere was air. The single-roll apparatus used consisted of a copper alloy cooling roll with a diameter of 300 mm, a high-frequency power supply for melting the samples, and a quartz crucible with a slotted nozzle at its tip. In this experiment, a slotted nozzle with a length of 10 mm and a width of 0.6 mm was used. The peripheral speed of the cooling roll was 24 m / s. The resulting ribbons had a thickness of approximately 25 μm, a width of 10 mm (depending on the length of the slotted nozzle), and a length of approximately 120 m.

[0075] The obtained ribbons were evaluated for saturation magnetic flux density and iron loss. The sample collection method and measurement conditions used for these property evaluations were the same as those in Example 1. The measurement results are shown in Table 3. The display method in Table 3 is the same as that in Table 1.

[0076] Furthermore, a 60 mm-wide ribbon was cast for embrittlement evaluation. A slot nozzle with a length of 60 mm and a width of 0.6 mm was used, and the peripheral speed of the cooling roll was 24 m / s. As a result, the thickness of the resulting ribbon was approximately 25 μm, the width was 60 mm (depending on the length of the slot nozzle), and the length was approximately 20 m. The workability of the Fe-based amorphous alloy ribbon was evaluated according to the tear embrittlement evaluation standard specified in JIS C 2534:2017. Specifically, a 2.4 m-long test ribbon was cut from the approximately 20 m-long cast ribbon. The test specimen was torn in a direction parallel to the casting direction at five locations: 12.7 mm and 25.4 mm from both casting edges in the width direction, and at the center in the width direction. The number of brittle spots with a size of approximately 6 mm or more, where the path and / or direction of the tear had changed, or where fragments had separated, was counted. The total number of brittle spots on one test piece was counted and a brittle code was determined based on the following criteria. A brittle code of 1 to 4 was considered to be acceptable. The results are shown in Table 3.

[0077] Brittle code 1: Total number of brittle spots is 0 Brittle code 2: Total number of brittle spots is 1-3 Brittle code 3: Total number of brittle spots is 4-6 Brittle code 4: 7-9 total brittle spots Brittle code 5: Total number of brittle spots is 10 or more

[0078] [Table 3]

[0079] As shown in Table 3, in all of Inventive Examples 26 to 52, the alloy composition satisfied the range of the present invention, and therefore the saturation magnetic flux density was 1.60 T or more, and the iron loss (iron loss W 13 / 50 ) was 0.095 W / kg or less, demonstrating high saturation magnetic flux density and low core loss at the same time. In addition, the brittleness rating for each was 1 to 4, demonstrating excellent workability.

[0080] On the other hand, in Comparative Examples 12 to 25, the alloy compositions did not satisfy the range of the present invention, and therefore the iron loss (iron loss W 13 / 50 ) exceeds 0.095 W / kg, the saturation magnetic flux density is less than 1.60 T, or the brittle code is 5.

[0081] In addition, when X-ray diffraction measurement was performed on the Fe-based amorphous alloy ribbons, no clear diffraction peaks were observed in any of the present invention examples 26 to 52 and the comparative examples 12 to 25, so it cannot be said that a crystalline phase was generated in the metal structure, and the entire structure was an amorphous phase.

[0082] Example 4 For the alloy shown in Inventive Example No. 26 in Table 3, alloys of various compositions in which part of the Fe was replaced with at least one of Ni, Cr, and Co were used to cast ribbons using the same equipment and conditions as in Example 1. The specific compositions of the alloys used are shown in Table 2. The thickness, width, and length of the ribbons obtained using a slot nozzle with a length of 10 mm and a width of 0.6 mm were approximately 25 μm, 10 mm, and 120 m, respectively. The thickness, width, and length of the ribbons obtained using a slot nozzle with a length of 60 mm and a width of 0.6 mm were approximately 25 μm, 60 mm, and 20 m, respectively. The saturation magnetic flux density, core loss, and tear embrittlement of the resulting ribbons were evaluated. The sample collection method and measurement conditions used to evaluate these properties were the same as in Example 3. The measurement results are shown in Table 4. The notation in Table 4 is the same as in Table 1.

[0083] [Table 4]

[0084] As is clear from the results of samples No. 53 to No. 59 in Table 4, even if part of the Fe is replaced with at least one of Ni, Cr, and Co in the range of 10.0 atomic % or less, the saturation magnetic flux density is 1.60 T or more, and the iron loss is reduced to W. 13 / 50It was found that the electrical resistance could be stably reduced to 0.095 W / kg or less. All samples had a brittleness rating of 2 to 3, demonstrating excellent workability. Furthermore, no clear diffraction peaks were observed in X-ray diffraction measurements of any of the samples, confirming that they were amorphous.

[0085] As explained above, the Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of the present invention contain Al, and the contents of B, Si, C, and P are optimized, and the Fe content is set to 78% or more, thereby achieving the iron loss (iron loss W 13 / 50 ) was 0.095 W / kg or less, and the saturation magnetic flux density was 1.60 T or more, demonstrating excellent soft magnetic properties.

Claims

1. In atomic percent, B: 8.0% or more and 18.0% or less, Si: 2.0% or more and 9.0% or less, C: 0.10% or more and less than 3.00%; Al: 0.005% or more and 1.50% or less, P: 0% or more and less than 1.00% Mn: 0% or more and 0.30% or less, Fe: 78.00% or more and 86.00% or less, Remainder: Impurities less than 0.1% It consists of The structure is amorphous, Saturation magnetic flux density is 1.60T or more, Iron loss at a magnetic flux density of 1.3T and a frequency of 50Hz is 0.095W / kg or less is An Fe-based amorphous alloy characterized by:

2. In atomic percent, The B content is 10.0% or more and 18.0% or less, The Si content is 2.0% or more and 6.0% or less, The C content is 0.10% or more and less than 3.00%; P content is 0% or more and 0.05% or less 2. The Fe-based amorphous alloy according to claim 1, wherein:

3. In atomic percent, The B content is 11.0% or more and 16.0% or less, The Si content is 2.0% or more and 4.0% or less, The C content is 0.10% or more and less than 3.00%; P content is 0% or more and 0.05% or less 2. The Fe-based amorphous alloy according to claim 1, wherein:

4. In atomic percent, The B content is 8.0% or more and 16.0% or less, The Si content is more than 2.0% and not more than 9.0%; The Al content is 0.005% or more and 1.00% or less, P content is 0.01% or more and less than 1.00% and The sum of the P and Al contents is 0.10% or more and 1.50% or less 2. The Fe-based amorphous alloy according to claim 1, wherein:

5. In atomic percent, The B content is 8.0% or more and 15.0% or less, The Si content is more than 3.0% and not more than 7.5%; The C content is 0.50% or more and less than 3.00%; The Al content is 0.01% or more and 0.80% or less, The P content is 0.01% or more and 0.80% or less, Fe content is 78.00% or more and 85.00% or less and The sum of the P and Al contents is 0.10% or more and 1.50% or less 2. The Fe-based amorphous alloy according to claim 1, wherein:

6. In atomic percent, The B content is 10.0% or more and 16.0% or less, The Si content is more than 2.0% and not more than 6.0%; The C content is 0.10% or more and less than 3.00%; The Al content is 0.01% or more and 1.00% or less, The P content is 0.01% or more and less than 1.00%; Fe content is 78.00% or more and 84.00% or less and The sum of the P and Al contents is 0.10% or more and 1.50% or less 2. The Fe-based amorphous alloy according to claim 1, wherein:

7. 7. The Fe-based amorphous alloy according to claim 1, wherein the Fe is substituted with at least one of Ni, Cr, and Co in an amount of 10.0 atomic % or less.

8. An Fe-based amorphous alloy ribbon made of the Fe-based amorphous alloy according to any one of claims 1 to 6.

9. An Fe-based amorphous alloy ribbon made of the Fe-based amorphous alloy according to claim 7.

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