Fe-based amorphous alloy ribbon

By optimizing the composition of Fe-based amorphous alloys with controlled B, Si, Mn, S, and N contents, the alloys exhibit improved workability and soft magnetic properties, suitable for transformer iron cores.

JP7719417B1Active Publication Date: 2025-08-06NIPPON STEEL CORPORATION
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Patent Information

Application Number
JP2024560380
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2024-04-22
Publication Date
2025-08-06
Estimated Expiration
2044-04-22

AI Technical Summary

Technical Problem

Fe-based amorphous alloy ribbons exhibit poor workability, leading to cracks during bending, which affects the yield and processing into iron cores for transformers.

Method used

Optimizing the composition of Fe-based amorphous alloys by controlling the content of elements such as B, Si, Mn, S, and N, with specific ranges to improve amorphous phase formation and thermal stability, while adding appropriate amounts of Mn and N to enhance soft magnetic properties and workability.

Benefits of technology

The optimized Fe-based amorphous alloys achieve a bending fracture diameter of 4 mm or less, maintaining high saturation magnetic flux density and low iron loss, enhancing their suitability for iron cores in transformers.

✦ Generated by Eureka AI based on patent content.

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Abstract

This Fe-based amorphous alloy contains, in atomic %, B: 8.0% to 18.0%, Si: 2.0% to 9.0%, Mn: 0.05% to 0.60%, Fe: 78.00% to 86.00%, S: 0.006% to 0.020%, N: 0.0010% to 0.2000%, with the remainder being impurities, and has an amorphous structure.
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Description

[Technical Field]

[0001] The present invention relates to an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon, and more particularly to an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that are excellent in workability. [Background technology]

[0002] Known methods for continuously producing ribbons or wires by rapidly cooling alloys 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 device 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] In particular, Fe-based amorphous alloys have relatively low iron loss and relatively high saturation magnetic flux density compared to non-Fe-based amorphous alloys, and are therefore considered promising for use in the iron cores of power transformers and high-frequency transformers.

[0004] Incidentally, Fe-based amorphous alloys are sometimes obtained as ribbons with a thickness of 0.1 mm or less. The Fe-based amorphous alloy ribbons are sometimes bent to be used for iron cores of power transformers, high-frequency transformers, etc. However, when Fe-based amorphous alloy ribbons, which have poor workability, are bent, cracks may occur at the bent portion. Therefore, in order to improve the yield when the ribbons are processed into iron cores, etc., the Fe-based amorphous alloy ribbons are required to have excellent workability.

[0005] Patent Document 1 describes an Fe-B-Si-C amorphous alloy ribbon having Fe as a base element and B, Si, and C as alloy constituent elements, and further having the following contents of impurities: P: 0.008% to 0.1%, Mn: 0.15% to 0.5%, and S: 0.004% to 0.05%, in weight percent.

[0006] Patent Document 2 describes an Fe-based amorphous alloy ribbon containing, in atomic percent, 5 to 25% B, 1 to 30% Si, 0.001 to 0.2% N, and the remainder being Fe and unavoidable impurities.

[0007] Patent Document 3 describes an amorphous alloy ribbon containing Fe, Si, B, C, Mn, S, and unavoidable impurities, and having a composition in which, when the total amount of Fe, Si, B, and C is taken as 100.0 atomic %, Si is 3.0 atomic % or more and 10.0 atomic % or less, B is 10.0 atomic % or more and 15.0 atomic % or less, and C is 0.2 atomic % or more and 0.4 atomic % or less, the Mn content is more than 0.12 mass % and less than 0.15 mass %, the S content is more than 0.0034 mass % and less than 0.0045 mass %, and the thickness is 10 μm or more and 40 μm or less and the width is 100 mm or more and 300 mm or less.

[0008] In Patent Document 1, it is said that by using B, Si, and C as alloy constituent elements and specifying the contents of P, Mn, and S elements, it becomes possible to use low-grade materials and reduce the alloy cost when producing this ribbon, but no consideration is given to improving the workability (bending fracture diameter).

[0009] Patent Document 2 describes that by adding N to Fe-B-Si and Fe-B-Si-C amorphous alloys, impurity elements (such as Al), which are said to promote crystallization, are concentrated in the surface oxide layer, thereby preventing crack propagation in the amorphous alloy ribbon and significantly improving workability, and also describes that the effect of adding N reduces the bending fracture diameter by about 40%, improving brittleness. However, there is no mention of adding S (sulfur).

[0010] Patent Document 3 describes that by adjusting the Mn and S contents in an Fe-B-Si-C amorphous alloy ribbon, molten metal can be continuously poured from a pouring nozzle for a long period of time, but does not consider at all how to improve workability (bending fracture diameter). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 9-95760 [Patent Document 2] Japanese Patent Application Publication No. 2006-316348 [Patent Document 3] International Publication No. 2016 / 084741 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that are excellent in workability. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention employs the following configuration. [1] in atomic percent, B: 8.0% or more and 18.0% or less, Si: 2.0% or more and 9.0% or less, Mn: 0.05% or more and 0.60% or less, Fe: 80.67 % or more and 86.00% or less, S: 0.006% or more and 0.020% or less, N: Contains 0.0010% or more and 0.2000% or less, the remainder being impurities, Fe-based amorphous alloy with an amorphous structure Thin ribbon . [2] The Fe-based amorphous alloy according to [1], wherein B is 13.0 atomic % or more and 18.0 atomic % or less. Thin ribbon . [3] The Fe-based amorphous alloy according to [1], wherein Si is 2.0 atomic % or more and 6.0 atomic % or less. Thin ribbon . [4] The Fe-based amorphous alloy according to [2], wherein Si is 2.0 atomic % or more and 6.0 atomic % or less. Thin ribbon. [5] The Fe-based amorphous alloy according to [1], wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less. Thin ribbon . [6] The Fe-based amorphous alloy according to [2], wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less. Thin ribbon . [7] The Fe-based amorphous alloy according to [3], wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less. Thin ribbon . [8] The Fe-based amorphous alloy according to [4], wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less. Thin ribbon . [9] N content relative to S content atom The Fe-based amorphous alloy according to [1], wherein the ratio (N / S) is 0.20 or more and 15 or less. Thin ribbon .

[10] The ratio of N content to S content atom The Fe-based amorphous alloy according to [2], wherein the ratio (N / S) is 0.20 or more and 15 or less. Thin ribbon .

[11] N content relative to S content atom The Fe-based amorphous alloy according to [3], wherein the ratio (N / S) is 0.20 or more and 15 or less. Thin ribbon .

[12] N content relative to S content atom The Fe-based amorphous alloy according to [4], wherein the ratio (N / S) is 0.20 or more and 15 or less. Thin ribbon .

[13] The Fe-based amorphous alloy according to any one of [1] to

[12] , wherein Fe is substituted with at least one element selected from Ni, Cr, and Co in an amount of 10.0 atomic % or less. Thin ribbon .

[14] Iron loss W when magnetized at a frequency of 50 Hz and a magnetic flux density of 1.3 T 13 / 50 The Fe-based amorphous alloy according to any one of [1] to

[12] , wherein the magnetic flux density is 0.100 W / kg or less and the saturation magnetic flux density is 1.60 T or more. Thin ribbon .

[15] Iron loss W when magnetized at a frequency of 50 Hz and a magnetic flux density of 1.3 T 13 / 50 The Fe-based amorphous alloy according to

[13] , wherein the magnetic flux density is 0.100 W / kg or less and the saturation magnetic flux density is 1.60 T or more. Thin ribbon .

[16] The bending fracture diameter is 4 mm or less; Any one of [1] to

[12] 2. The Fe-based amorphous alloy ribbon according to claim 1. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that are excellent in workability. DETAILED DESCRIPTION OF THE INVENTION

[0015] The inventors have found that an Fe-based amorphous alloy with excellent workability, such as a bending fracture diameter of 4 mm or less, can be obtained while improving amorphous-forming ability by controlling the content of S, an element that deteriorates brittleness, and adjusting the contents of amorphous-forming elements such as B, Si, and N. Furthermore, they have found that by adding Mn in the range of 0.05 atomic % to 0.60 atomic %, it is possible to achieve both excellent soft magnetic properties and workability.

[0016] Hereinafter, an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon according to embodiments of the present invention will be described.

[0017] In this embodiment, "excellent processability" means that when the Fe-based amorphous alloy is made into a ribbon, the bending fracture diameter is small, and "excellent soft magnetic properties" means that the alloy has low iron loss and high saturation magnetic flux density.

[0018] The Fe-based amorphous alloy of this embodiment contains, in atomic %, B: 8.0% to 18.0%, Si: 2.0% to 9.0%, Mn: 0.05% to 0.60%, Fe: 78.00% to 86.00%, S: 0.006% to 0.020%, N: 0.0010% to 0.2000%, with the remainder being impurities, and has an amorphous structure.

[0019] Furthermore, the Fe-based amorphous alloy of this embodiment may contain B: 13.0 atomic % or more and 18.0 atomic % or less. The Fe-based amorphous alloy of this embodiment may contain Si: 2.0 atomic % or more and 6.0 atomic % or less.

[0020] Furthermore, when the Fe-based amorphous alloy of this embodiment contains S and N, the ratio of the amount of N to the amount of S (N / S) may be 0.20 or more and 15 or less. Furthermore, in the Fe-based amorphous alloy of this embodiment, Fe may be substituted with at least one element selected from Ni, Cr, and Co in a range of 10.0 atomic % or less. The Fe-based amorphous alloy ribbon of this embodiment is made of the above-mentioned Fe-based amorphous alloy.

[0021] First, the reasons for limiting the content of each element in the Fe-based amorphous alloy of this embodiment will be described.

[0022] B is added to the Fe-based amorphous alloy of this embodiment to improve the amorphous phase formation and thermal stability of the amorphous phase. By optimizing the content of this element, the alloy structure can be stably amorphous, thereby 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 atomic %, the amorphous phase formation 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 the saturation magnetic flux density at 1.60 T or higher while maintaining the iron loss at 0.100 W / kg or lower. On the other hand, if the B content exceeds 18.0 atomic %, the amorphous phase formation ability is not improved, and it becomes difficult to stably maintain the saturation magnetic flux density at 1.60 T or higher. Therefore, the B content is set to 8.0 atomic % or higher and 18.0 atomic % or lower. The lower limit of B is preferably 10.0 atomic %, more preferably 13.0 atomic %. The upper limit of B is preferably 16.0 atomic %, and more preferably 15.0 atomic %.

[0023] Like B, Si is added to the Fe-based amorphous alloy of this embodiment to improve the amorphous phase formation and thermal stability of the amorphous phase. By optimizing the Si content, the alloy structure can be stably amorphous, thereby further improving soft magnetic properties. If the Si content is less than 2.0 atomic %, the amorphous phase formation 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 the saturation magnetic flux density at 1.60 T or more while maintaining the iron loss at 0.100 W / kg or less. On the other hand, if the Si content exceeds 9.0 atomic %, the amorphous phase formation ability is not improved, and it becomes difficult to stably maintain the iron loss at 0.100 W / kg or less. Therefore, the Si content is set to 2.0 atomic % or more and 9.0 atomic % or less. The lower limit of Si is preferably 3.0 atomic %, more preferably 4.0 atomic %. The upper limit of Si is preferably 6.0 atomic %, more preferably 5.0 atomic %, and particularly preferably less than 5.0 atomic %.

[0024] Mn is added to the Fe-based amorphous alloy of this embodiment to improve its soft magnetic properties. By optimizing the Mn content, it is possible to stably maintain the saturation magnetic flux density at 1.60 T or more while stably maintaining the core loss at 0.100 W / kg or less. If the Mn content is less than 0.05 atomic %, it becomes difficult to stably maintain the saturation magnetic flux density at 1.60 T or more while stably maintaining the core loss at 0.100 W / kg or less. On the other hand, if the Mn content exceeds 0.60 atomic %, it becomes difficult to stably maintain the core loss at 0.100 W / kg or less. Therefore, the Mn content is set to 0.05 atomic % or more and 0.60 atomic % or less. The lower limit of Mn is preferably 0.10 atomic %, more preferably 0.20 atomic %. The upper limit of Mn is preferably 0.50 atomic %, more preferably 0.40 atomic %.

[0025] In Fe-based amorphous alloys, if the Fe content is 70 atomic % 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 atomic % or more. On the other hand, if the Fe content exceeds 86.00 atomic %, 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 It becomes difficult to stably obtain a thermal conductivity of 0.100 W / kg or less. Therefore, in the Fe-based amorphous alloy of this embodiment, the Fe content is set to 78.00 atomic % or more and 86.00 atomic % or less. The lower limit of Fe is preferably 79.00 atomic %, more preferably 80.00 atomic %. The upper limit of Fe is preferably 85.00 atomic %, more preferably 84.00 atomic %.

[0026] In the Fe-based amorphous alloy of this embodiment, by substituting at least one of Ni, Cr, and Co in a range of 10.0 atomic % or less for a portion of Fe, it is possible to improve soft magnetic properties such as core loss while maintaining a high saturation magnetic flux density. The reason for setting an upper limit on the amount of substitution by these elements is that if the amount exceeds 10.0 atomic %, the saturation magnetic flux density decreases and the raw material cost increases. When Fe is substituted with one or more of Ni, Cr, and Co, the total content of Ni, Cr, and Co and the Fe content may be 78.00 atomic % or more and 86.00 atomic % or less, or may be 79.00 atomic % or more and 84.00 atomic % or less.

[0027] Furthermore, the Fe-based amorphous alloy of this embodiment must contain, in atomic percent, S: 0.006% or more and 0.020% or less, and N: 0.0010% or more and 0.2000% or less.

[0028] S is an element that deteriorates the brittleness of the Fe-based amorphous alloy of this embodiment. By optimizing the S content, it is possible to make the bending fracture diameter of the Fe-based amorphous alloy ribbon 4 mm or less. Therefore, the S content is set to 0.006 atomic % or more and 0.020 atomic % or less. The upper limit of S is preferably 0.016 atomic %, more preferably 0.014 atomic %, and even more preferably 0.010 atomic % or less.

[0029] N is contained in the Fe-based amorphous alloy of this embodiment to improve amorphous-forming ability and workability. Optimizing the N content makes it possible to reduce the bending fracture diameter of an Fe-based amorphous alloy ribbon to 4 mm or less. If the N content is less than 0.0010 atomic %, the effect of improving workability cannot be obtained. On the other hand, if the N content exceeds 0.2000 atomic %, the effect of amorphous-forming ability saturates and iron loss may increase. Therefore, the N content is set to 0.0010 atomic % or more and 0.2000 atomic % or less. Preferably, the N content is set to 0.0020 atomic % or more. More preferably, the N content is set to 0.0030 atomic % or more. Preferably, the N content is set to 0.1500 atomic % or less. More preferably, the N content is set to 0.1000 atomic % or less.

[0030] When the Fe-based amorphous alloy of this embodiment contains S and N, the ratio of the amount of N to the amount of S (atomic ratio) (N / S) may be 0.20 or more and 15 or less. By setting the ratio of the amount of S to the amount of N (N / S) to 0.20 or more and 15 or less, the processability can be further improved. In addition, the soft magnetic properties can also be improved. The lower limit of (N / S) may be 0.40, or even 0.60. The upper limit of (N / S) may be 13, or even 11.

[0031] The balance in the Fe-based amorphous alloy according to this embodiment is impurities. When a steel material is used as the Fe source, the Fe-based amorphous alloy according to this embodiment may contain impurity elements contained in the steel material as impurities. For example, the alloy may contain impurities such as C, P, Al, Ti, and O in a total amount of less than 0.10 atomic %. The approximate amounts of each element contained as an impurity are C less than 0.03 atomic %, P less than 0.01 atomic %, Al less than 0.01 atomic %, Ti less than 0.005 atomic %, and O less than 0.04 atomic %.

[0032] The Fe-based amorphous alloy of this embodiment has an amorphous structure, which allows it to obtain excellent soft magnetic properties. Whether or not the alloy has an amorphous structure can be confirmed, for example, by 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. Here, "no clear diffraction peak is obtained in the X-ray diffraction measurement" means that there is no peak with a half-width (full width at half maximum) of 4° or less of the diffraction peak of α-Fe(110).

[0033] When the saturation magnetic flux density and iron loss of the Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of this embodiment are measured by the method described below, the saturation magnetic flux density is 1.60 T or more, the magnetic flux density is 1.3 T, and the iron loss (iron loss W 13 / 50 ) is preferably 0.100 W / kg or less. This allows the Fe-based amorphous alloy and the Fe-based amorphous alloy ribbon of the present embodiment to have excellent soft magnetic properties.

[0034] 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 Hz. 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 width center of each of the ribbon samples from the six locations mentioned above.

[0035] Furthermore, the Fe-based amorphous alloy ribbon of this embodiment can have a bending fracture diameter of 4 mm or less. The bending fracture diameter can be obtained in accordance with the bending test method for metallic materials of JIS Z 2248: 2006, by placing a ribbon made of an Fe-based amorphous alloy in a bending tester, pressing both ends of the test piece together until they come into close contact, and measuring the diameter of the test piece at fracture (bending fracture diameter).

[0036] The Fe-based amorphous alloy and the method for producing the Fe-based amorphous alloy ribbon according to this embodiment will be described below. The Fe-based amorphous alloy according to this embodiment can usually be obtained in the form of a ribbon. This Fe-based amorphous alloy ribbon can be produced by melting an alloy having 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, for example, 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 surface or inner surface of the roll.

[0037] 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.

[0038] 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.

[0039] The Fe-based amorphous alloy of this embodiment can be in the form of a powder in addition to a ribbon. To obtain a powdered Fe-based amorphous alloy, a method can be employed in which the molten alloy or droplets of the molten alloy are ejected at high speed from the nozzle of a crucible filled with the molten alloy having the above-described composition into a rotating roll or a liquid such as cooling water, thereby causing rapid solidification.

[0040] By the above-mentioned method, it is possible to obtain Fe-based amorphous alloy powder having excellent soft magnetic properties.

[0041] 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 then sintered and integrated as necessary, and can be used for applications such as power transformers, high-frequency transformers, and coil cores.

[0042] As described above, according to the Fe-based amorphous alloy and the Fe-based amorphous alloy ribbon of the present embodiment, the workability can be improved by optimizing the contents of B and Si, adding an appropriate amount of Mn, further adding S and N, and further setting the Fe content to 78.00% or more.

[0043] In addition, in the Fe-based amorphous alloy and the Fe-based amorphous alloy ribbon of this embodiment, the iron loss (iron loss W 13 / 50 ) is preferably 0.100 W / kg or less and the saturation magnetic flux density is preferably 1.60 T or more. This allows the Fe-based amorphous alloy and the Fe-based amorphous alloy ribbon of the present embodiment to exhibit excellent soft magnetic properties. This allows them to be suitably used for the iron cores of power transformers, high-frequency transformers, etc.

[0044] Furthermore, the Fe-based amorphous alloy ribbon of this embodiment can have a bending fracture diameter of 4 mm or less, which prevents the alloy ribbon from being damaged when the Fe-based amorphous alloy ribbon is processed into iron cores of power transformers, high-frequency transformers, etc., thereby improving the productivity of iron cores for power transformers and high-frequency transformers. The bending fracture diameter of the Fe-based amorphous alloy ribbon of this embodiment is more preferably 2 mm or less. [Example]

[0045] Examples of the present invention will be described below.

[0046] Example 1 Fe-based amorphous alloy ribbons were produced by melting alloys with the compositions shown in Tables 1A and 1B 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 300 mm diameter copper alloy cooling roll, 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 measuring 10 mm in length and 0.6 mm in width was used. The peripheral speed of the cooling roll was 24 m / s. The resulting ribbons were approximately 20 μm thick, 10 mm wide (depending on the length of the slotted nozzle), and approximately 100 m long.

[0047] X-ray diffraction measurement was 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 measurement was Co-Kα (wavelength λ = 0.17902 nm), and the scan range was 2θ = 10° to 120°. Whether a crystalline phase was formed in the metal structure was determined from the shape of the X-ray diffraction pattern.

[0048] 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 Hz. 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.

[0049] The saturation magnetic flux density and iron loss measurement results are shown in Tables 1A and 1B as average values of data at six locations.

[0050] Furthermore, the bending fracture diameter of the Fe-based amorphous alloy ribbon was measured. The bending fracture diameter was measured in accordance with JIS Z 2248:2006, a bending test method for metallic materials, by placing the Fe-based amorphous alloy ribbon on a bending tester and measuring the bending fracture diameter at break. The results are shown in Table 1A and Table 1B.

[0051] [Table 1A]

[0052] [Table 1B]

[0053] As shown in Table 1A, in all of Inventive Examples 1 to 22, 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 0.100 W / kg or less, demonstrating high saturation magnetic flux density and low iron loss at the same time. In addition, the bending fracture diameter was 4 mm or less, and workability was also good.

[0054] On the other hand, as shown in Table 1B, in Comparative Examples 101 to 113, the alloy compositions did not satisfy the range of the present invention, and therefore the iron loss (iron loss W 13 / 50 ) exceeds 0.100 W / kg or the saturation magnetic flux density becomes less than 1.60 T.

[0055] That is, Comparative Example 101 had a low Fe content and a saturation magnetic flux density of less than 1.60T. In Comparative Example 102, the Fe content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0056] Comparative Example 103 has a low B content and low iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg. In Comparative Example 104, the B content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0057] Comparative Example 105 has a low Si content and low iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg. In Comparative Example 106, the Si content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0058] Comparative Example 107 has a low Mn content and low iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg. In Comparative Example 108, the Mn content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0059] In Comparative Example 109, the S content was excessive, and the bending fracture diameter exceeded 4 mm. 13 / 50 ) exceeded 0.100W / kg.

[0060] Comparative Example 110 had a low N content and the bending fracture diameter exceeded 4 mm. 13 / 50 ) exceeded 0.100W / kg. In Comparative Example 111, the N content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0061] In Comparative Example 112, the S content was excessive, and the bending fracture diameter exceeded 4 mm. 13 / 50 ) exceeded 0.100W / kg. In Comparative Example 113, the N content was excessive, and the iron loss (iron loss W 13 / 50 ) exceeded 0.100W / kg.

[0062] 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 22 and comparative examples 101 to 113, so it cannot be said that a crystalline phase was generated in the metal structure, and the entire structure was an amorphous phase.

[0063] Example 2 For each of the alloys shown in No. 1 of Table 1A, 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, core loss, and bending fracture diameter of the obtained ribbons were evaluated. The sample collection method and measurement conditions used for these property evaluations 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 Tables 1A and 1B.

[0064] [Table 2]

[0065] As is clear from the results of samples No. 23 to No. 29 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 bending fracture diameter was 4 mm or less, and workability was also good. Furthermore, no clear diffraction peaks were observed in X-ray diffraction measurements of any of the samples, confirming that they were amorphous.

[0066] As is clear from the above examples, it has become clear that the Fe-based amorphous alloy of the present invention can be made more workable by optimizing the contents of B and Si, adding an appropriate amount of Mn, further adding S and N, and further increasing the Fe content to 78.00% or more. In addition, the iron loss (W 13 / 50 ) is 0.100 W / kg or less, and the saturation magnetic flux density is 1.60 T or more, demonstrating excellent soft magnetic properties, making it suitable for use in the iron cores of power transformers and high-frequency transformers.

[0067] It was also revealed that the Fe-based amorphous alloy ribbon of the present invention has a bending fracture diameter of 4 mm or less. 13 / 50 ) was found to be 0.100 W / kg or less, and the saturation magnetic flux density was found to be 1.60 T or more. This means that when processing the Fe-based amorphous alloy ribbon into iron cores for power transformers and high-frequency transformers, there is no risk of the alloy ribbon being damaged, and it has become clear that the productivity of iron cores for power transformers and high-frequency transformers can be improved. [Industrial Applicability]

[0068] The Fe-based amorphous alloy and Fe-based amorphous alloy ribbon of the present disclosure have excellent workability and therefore high industrial applicability.

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, Mn: 0.05% or more and 0.60% or less, Fe: 80.67% or more and 86.00% or less, S: 0.006% or more and 0.020% or less, N: 0.0010% or more and 0.2000% or less; the remainder being impurities, An Fe-based amorphous alloy ribbon having an amorphous structure.

2. 2. The Fe-based amorphous alloy ribbon according to claim 1, wherein B is 13.0 atomic % or more and 18.0 atomic % or less.

3. 2. The Fe-based amorphous alloy ribbon according to claim 1, wherein Si is 2.0 atomic % or more and 6.0 atomic % or less.

4. 3. The Fe-based amorphous alloy ribbon according to claim 2, wherein Si is 2.0 atomic % or more and 6.0 atomic % or less.

5. 2. The Fe-based amorphous alloy ribbon according to claim 1, wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less.

6. 3. The Fe-based amorphous alloy ribbon according to claim 2, wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less.

7. 4. The Fe-based amorphous alloy ribbon according to claim 3, wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less.

8. 5. The Fe-based amorphous alloy ribbon according to claim 4, wherein N is 0.0030 atomic % or more and 0.2000 atomic % or less.

9. 2. The Fe-based amorphous alloy ribbon according to claim 1, wherein the atomic ratio of the amount of N to the amount of S (N / S) is 0.20 or more and 15 or less.

10. 3. The Fe-based amorphous alloy ribbon according to claim 2, wherein the atomic ratio of the amount of N to the amount of S (N / S) is 0.20 or more and 15 or less.

11. 4. The Fe-based amorphous alloy ribbon according to claim 3, wherein the atomic ratio of the amount of N to the amount of S (N / S) is 0.20 or more and 15 or less.

12. 5. The Fe-based amorphous alloy ribbon according to claim 4, wherein the atomic ratio of the amount of N to the amount of S (N / S) is 0.20 or more and 15 or less.

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

14. Iron loss W when magnetized at a frequency of 50 Hz and a magnetic flux density of 1.3 T 13/50 The Fe-based amorphous alloy ribbon according to any one of claims 1 to 12, having a saturation magnetic flux density of 1.60 T or more and a magnetic flux density of 0.100 W / kg or less.

15. Iron loss W when magnetized at a frequency of 50 Hz and a magnetic flux density of 1.3 T 13/50 The Fe-based amorphous alloy ribbon according to claim 13, wherein the magnetic flux density is 0.100 W / kg or less and the saturation magnetic flux density is 1.60 T or more.

16. The Fe-based amorphous alloy ribbon according to any one of claims 1 to 12, wherein the bending fracture diameter is 4 mm or less.

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