JP2018178168A - Fe-based amorphous alloy and Fe-based amorphous alloy ribbon - Google Patents

Abstract

[Problem] To provide an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that can achieve even lower iron loss. [Solution] An Fe-based amorphous alloy characterized by having B of 10.0% or more and 14.0% or less, Si of more than 6.0% and 8.0% or less, C of more than 1.0% and 4.0% or less, and the balance being Fe and unavoidable impurities. [Selected Figure] None

Description

  The present invention relates to Fe-based amorphous alloys and Fe-based amorphous alloy ribbons used for iron cores of power transformers, high-frequency transformers, and the like.

  A centrifugal quenching method, a single roll method, a twin roll method, and the like are known as methods for continuously producing ribbons and wires by quenching an alloy from a molten state. According to these methods, molten metal is rapidly solidified from an orifice or the like on an inner peripheral surface or an outer peripheral surface of a metal drum rotating at high speed to manufacture a thin strip or a wire. Further, by properly selecting the alloy composition, an amorphous alloy similar to liquid metal can be obtained, and a material having excellent magnetic properties or mechanical properties can be produced.

  Many components have been proposed as amorphous alloys obtained by such rapid solidification. For example, in Patent Document 1, at least one of Fe, Ni, Cr, Co, and V at 60% to 90%, at least one of P, C, and B at 10 to 30%, Al, Si in atomic%. At least one of Sn, Sb, Ge, In, and Be has been proposed as an alloy component consisting of 0.1 to 15%. The technology described in Patent Document 1 proposes an alloy component from which an amorphous phase can be obtained, and in particular, proposes a component focusing only on so-called magnetic properties limited to applications such as iron cores such as power transformers and high frequency transformers. is not.

After that, many alloy components as amorphous alloys focusing on magnetic properties have been proposed. For example, Patent Document 2 proposes an alloy component consisting of 75 to 78.5% of Fe, 4 to 10.5% of Si, and 11 to 21% of B in atomic percent.
On the other hand, in Patent Document 3, 70 to 90% of at least one of Fe and Co, and the balance are at least one of B, C, and P, and unavoidable impurities, and the Fe and Co content is Ni can replace up to 3/4 of Ni, V, Cr, Mn, Cu, Mo, Nb, Ta, W up to 1⁄4 of that, and B, C, P content, Si of 3/5 Alloy components have been proposed which can be substituted up to one third with Al.

  Among the amorphous alloy components proposed in Patent Documents 1 and 3, the iron loss which is an energy loss is low, the saturation magnetic flux density and the magnetic permeability are high, and further, an amorphous phase can be obtained stably, etc. For this reason, for example, FeSiB-based amorphous alloys as shown in Patent Document 2 have come to be considered promising as applications such as iron cores of power transformers and high frequency transformers.

  Since then, the development of alloy components of Fe-based amorphous alloys having excellent soft magnetic properties has been advanced focusing on the FeSiB-based. That is, further development of reduction of iron loss in the FeSiB-based amorphous alloy was actively performed, and many results were produced.

The improvement of the core loss in the amorphous alloy is considerably advanced, for example, stabilized by the core loss W _13/50 ( _core loss at a magnetic flux density of 1.3 T, frequency 50 Hz) by single plate measurement according to Patent Documents 4 and 5. To achieve a low iron loss of 0.10 W / kg or less.

  That is, the present inventors, for example, refer to Patent Document 4 in the atomic percent, 70% to 86% of Fe, 7% to 20% of B, 1% to 19% of Si, and 4% or less of C. We have proposed an alloy component that contains the balance and the remaining inevitable impurities.

  On the other hand, in Patent Document 5, the present inventors contain, for example, 7% to 20% of B, 1% to 19% of Si, and 0.02% to 4% of C in atomic%, and the balance We proposed an alloy component consisting of Fe and unavoidable impurities.

  Furthermore, the inventors of the present invention are, for example, Patent Document 6, and in atomic percent, Fe 80% to 82%, B 12% to 16%, Si 2% to 7%, C 0.003. We have proposed an alloy component that contains 1% or more and 2% or less and the balance is inevitable impurities.

  Thereafter, proposals as shown in Patent Documents 7 and 8 were also made. That is, in Patent Document 7, for example, at atomic percent, Fe is 78% to 86%, at least one of Ni and Cr is 0.01% to 5%, B is 7% to 20%, and Si is 0 We have proposed an alloy component that contains .001% or more and 5% or less, and the balance consists of unavoidable impurities.

  On the other hand, Patent Document 8 contains, for example, 76% to 84% of Fe, 8% to 18% of B, 12% or less of Si, and 0.01% to 3% of C in atomic percent, We proposed an alloy ribbon composed of residual impurities and having a C segregation layer in the depth direction from 2 to 20 nm from the surface of the free surface and roll surface.

JP-A-49-91014 Japanese Patent Application Laid-Open No. 57-116750 Japanese Patent Application Laid-Open No. 61-30649 JP-A-8-283920 JP-A-9-95760 JP, 2006-312777, A Unexamined-Japanese-Patent No. 2006-45660 Unexamined-Japanese-Patent No. 2006-45662

  However, although iron loss reduction development in amorphous alloys has been considerably advanced so far, further improvement in iron loss is strongly demanded. The issue of improving energy loss in electricity is a rather pressing one.

  An object of the present invention is to provide an Fe-based amorphous alloy and a Fe-based amorphous alloy ribbon capable of realizing further reduction of iron loss, in order to meet the need for further reduction of iron loss. is there.

Among the constituent elements of the various alloy components proposed so far, the present inventor mainly uses Fe described in, for example, Patent Documents 4 and 5 described above, and a component system containing B, Si, and C as alloy elements. We examined and experimented on the further reduction of iron loss. Then, the main of Fe, additive element B, Si, the component system consisting mainly of C, result of detailed experiments, the iron loss (iron loss _{W 13/50)} is stable 0.085W / kg or less The component range of the amorphous alloy to be Then, based on this finding, studies were repeated to complete the present invention.

The present invention has been made based on the above findings, and the summary thereof is as follows.
(1) In the present invention, B is not less than 10.0% and not more than 14.0%, Si is not less than 6.0% and not more than 8.0%, C is not less than 1.0% and not more than 4.0% in atomic%. The present invention relates to a Fe-based amorphous alloy characterized in that the balance is composed of Fe and unavoidable impurities.
(2) In the present invention, at atomic%, B is 10.0% or more and 14.0% or less, Si is more than 6.0% and 8.0% or less, C is more than 1.0% and 4.0% or less, And, the total content of B, Si, and C is 17.0% or more and 19.0% or less, or 23.0% or more and 25.0% or less, and the balance is composed of Fe and unavoidable impurities. The invention relates to a Fe-based amorphous alloy.
(3) In the present invention, at least one or more of Ni, Cr, and Co are substituted for Fe of the Fe-based amorphous alloy described in (1) or (2) in a range of 10.0 atomic% or less Fe-based amorphous alloy characterized by
(4) The present invention may be any magnetic flux density 1.3 T, the iron loss at a frequency 50 Hz (iron loss _{W 13/50)} is equal to or less than 0.085W / kg (1) ~ ( 3) The present invention relates to the Fe-based amorphous alloy according to one aspect.
(5) The present invention relates to an Fe-based amorphous alloy ribbon comprising the Fe-based amorphous alloy according to any one of (1) to (4).

The present invention can provide iron loss (iron loss _{W 13/50)} stable Fe-based amorphous alloy and Fe-based amorphous alloy ribbon can be below 0.085W / kg by the.

Hereinafter, the Fe-based amorphous alloy according to the present invention will be described in detail.
The feature of the Fe-based amorphous alloy of the present embodiment is to find a component range in which the iron loss becomes extremely low by optimizing the content of these constituent elements in the Fe, B, Si, and C alloys. iron loss _{W 13/50)} is in that realize that the following stable 0.085W / kg. Further, the Fe-based amorphous alloy of the present embodiment is to realize further improvement of the soft magnetic characteristics by substituting a part of Fe which is the base with Ni, Cr and Co. In addition, iron loss _W13 / 50 here is an iron loss in magnetic flux density 1.3T and the frequency of 50 Hz in the iron loss measurement by a single board.

Moreover, the measurement of iron loss W _13/50 is performed as follows. The molten alloy is quenched and solidified to produce an amorphous alloy ribbon. Iron loss W _13/50 is measured from a plurality of measurement points over the entire length of the obtained amorphous alloy ribbon, and the maximum value among them is iron loss W _13/50 . The number of measurement points is not particularly limited, but may be, for example, six or more. Although the iron loss W _13/50 of the amorphous alloy ribbon varies somewhat, in the present embodiment the maximum value thereof is 0.085 W / kg or less, so it is possible to stably maintain a low iron loss. It becomes possible to obtain a crystalline alloy. Iron loss _{W 13/50} is more preferably not more than 0.083W / kg.

  First, the reason for limiting the content of each element in the Fe-based amorphous alloy of the present embodiment will be described.

  B, Si and C are added in the Fe-based amorphous alloy of the present embodiment to improve the formation of the amorphous phase and the thermal stability. It has been found that by optimizing the content of these elements, it is possible to further improve the iron loss.

That is, in order to realize further reduction of iron loss based on, for example, Patent Documents 4 and 5, the inventors examined in detail the relationship between the content of B, Si and C and iron loss, and these elements in the area where combined with optimized content found that iron loss _{W 13/50} becomes less stable 0.085W / kg.
Therefore, in the present invention, the contents of B, Si and C are limited as follows. That is, in atomic percent, B is limited to 10.0% to 14.0%, Si to 6.0% to 8.0%, and C to 1.0% to 4.0%.

Furthermore, the iron loss W _13/50 becomes stable by setting the total content of B, Si and C to more than 17.0% and 19.0% or less or 23.0% or more and 25.0% or less It is also possible to make it 0.083 W / kg or less.

On the other hand, at least one element of B, Si and C is atomic%, B less than 10.0% or 14.0%, Si less than 6.0% or more than 8.0%, C There becomes 1.0% or less, or 4.0 percent, it becomes difficult to 0.085W / kg or less core loss _{W 13/50} stably.

  In the Fe-based amorphous alloy of the present embodiment, improvement in iron loss can also be realized by substituting a part of Fe with at least one of Ni, Cr, and Co in the range of 10.0 atomic% or less. The reason why an upper limit is given to the substitution amount by these elements is that the raw material cost is increased when the amount exceeds 10.0 atomic%.

  The balance of the Fe-based amorphous alloy of the present embodiment is Fe and unavoidable impurities. Here, in the Fe-based amorphous alloy, the content of Fe is important in terms of magnetic flux density, and a saturation magnetic flux density of about 1.5 T or more is usually required. The saturation magnetic flux density is uniquely determined by the Fe content in the alloy, and the higher the Fe content, the higher the saturation magnetic flux density. Therefore, in order to make the saturation magnetic flux density about 1.5 T or more, the content of Fe is preferably 75.0% or more in atomic%. The upper limit of the Fe content is preferably 86.0 atomic% or less. When the Fe content exceeds 86.0 atomic%, it is difficult to form an amorphous phase.

  The Fe-based amorphous alloy of the present embodiment can usually be obtained in the form of a ribbon. The Fe-based amorphous alloy ribbon melts the alloy composed of the components described in the above-described embodiment, and spouts the molten metal onto a cooling plate moving at high speed through a slot nozzle etc. It can be manufactured by a rapid solidification method, for example, a single roll method or a double roll method. The rolls used in these rolling methods are made of metal, and the rapid solidification of the alloy is possible by rotating the rolls at high speed and causing the molten metal to collide with the surface of the rolls or the inner surface of the rolls.

  Single-roll equipment includes centrifugal quench equipment using the inner wall of the drum, equipment using an endless type belt, and auxiliary rollers and roll surface temperature control equipment that are these improvements, under reduced pressure or under vacuum, Or casting equipment in inert gas is also included.

  In the present embodiment, the dimensions such as the thickness and the width of the ribbon are not particularly limited, but the thickness of the ribbon is preferably, for example, 10 μm to 100 μm. The plate width is preferably 10 mm or more.

  The Fe-based amorphous alloy ribbon obtained as described above can be used as an application for an iron core or the like in a power transformer or a high frequency transformer.

In addition to the ribbon, the Fe-based amorphous alloy of the present embodiment can be made into powder. In that case, a method is adopted in which the molten alloy or molten alloy droplets are ejected at high speed into a liquid such as a rotating roll or cooling water from a nozzle of a crucible filled with molten alloy of the above composition and quenched rapidly. can do.
By the above-described method, it is possible to obtain an Fe-based amorphous alloy powder excellent in soft magnetic properties.

  The Fe-based amorphous alloy powder thus obtained is compacted by a mold or the like into a desired shape, and optionally sintered and integrated as required, to form a power transformer, a high frequency transformer, or a coil. It can be applied to applications such as iron cores.

  Whether or not the Fe-based amorphous alloy of the present embodiment has an amorphous structure can be confirmed, for example, by X-ray diffraction measurement using an X-ray diffractometer using an Fe tube. That is, when a clear diffraction peak can not be obtained in X-ray diffraction measurement, it can be confirmed that the Fe-based amorphous alloy has an amorphous structure.

Examples will be described below.
Example 1
The alloys of the various components shown in Table 1 below were melted in an argon atmosphere and cast with a single roll apparatus to produce a ribbon. The casting atmosphere was in the atmosphere. And the soft magnetic property was investigated about the obtained thin strip. The single roll apparatus used is composed of a copper alloy cooling roll with a diameter of 300 mm, a high frequency power supply for sample dissolution, and a quartz crucible with a slot nozzle at its tip.

  In this experiment, a slot nozzle with a length of 20 mm and a width of 0.6 mm was used. The circumferential speed of the cooling roll was 24 m / sec. As a result, the thickness of the obtained ribbon was about 25 μm, and the plate width was 20 mm because it depends on the length of the slot nozzle, and the length was about 50 m.

The core loss of the obtained ribbon was measured using SST (Single Strip Tester). The core loss measurement conditions are a magnetic flux density of 1.3 T and a frequency of 50 kHz. All of these samples for characteristic measurement were taken from six places over the entire length of one lot, and the sample for iron loss measurement was a thin strip sample cut to a length of 120 mm. These ribbon samples for core loss measurement were subjected to measurement by annealing in a magnetic field at 360 ° C. for 1 hour. The atmosphere during annealing was nitrogen. The measurement results of iron loss show the maximum values of data at six places in Table 1.
On the other hand, the saturation magnetic flux density was measured using a VSM apparatus (vibrating sample magnetometer). The samples for the VSM apparatus were thin pieces collected from the center of the width of all the thin strip samples from the above six locations.

  Sample No. in Table 1 As apparent from the results of 1 to 20, B is contained in the range of 10.0 atomic% or more and 14.0 atomic% or less, Si is more than 6.0 atomic% and 8.0 atomic% or less, C is more than 1.0 atomic% An Fe-based amorphous alloy ribbon having good soft magnetic characteristics such as iron loss of 0.085 W / kg or less at a magnetic flux density of 1.3 T and a frequency of 50 Hz by setting the range of the present invention of not more than .0 atomic% It turned out that it could be obtained. Furthermore, sample No. 1 of Table 1 1, No. 3, No. 4, no. 6, No. 8, No. 10, no. 11, No. 13-No. As is apparent from the results of 18, the total content of B, Si and C is more than 17.0 atomic% and 19.0 atomic% or less, or 23.0 atomic% or more and 25.0 atomic% or less It has been found that an Fe-based amorphous alloy ribbon having soft magnetic properties with a core loss being stable and 0.083 W / kg or less can be obtained. Also, for sample no. The saturation magnetic flux density of 1 to 20 was 1.5 T or more. Furthermore, sample no. From 1 to 20, no clear diffraction peak was observed in the X-ray diffraction measurement, and it was confirmed that the sample was amorphous.

On the other hand, for sample no. Of the comparative examples shown in 21 to 29, the sample No. 1. 21, no. In No. 27, since a wave occurred on the surface and a good ribbon was not obtained, the iron loss could not be measured (indicated by "-" in the column of "iron loss" in Table 1).
Sample No. No. 21 is an example where the B content is below the lower limit of 10.0 atomic% of the desired range. 27 is an example in which the B content is below the lower limit 10.0 atomic percent of the desirable range, and the Si content becomes the lower limit 6.0 atomic percent or less of the desirable range.

  On the other hand, for sample no. 22-No. 26, no. 28, No. In No. 29, even if a thin band was obtained, the characteristic which an iron loss satisfied 0.085 W / kg or less was not obtained.

Sample No. 22 is an example in which the B content exceeds the upper limit of 14.0 atomic% in the desired range and the iron loss is increased; No. 23 is an example in which the iron loss increases due to the Si content being below the lower limit of 6.0 atomic% of the desired range, No. 24 is an example in which the iron loss is increased by exceeding the upper limit of 8.0 atomic% of the desirable range of the Si content.
On the other hand, for sample no. No. 25 is an example in which the C content is 1.0 atomic% or less of the lower limit and the iron loss is increased, No. 26 is an example in which the C content exceeds the upper limit of 4.0 atomic% and the iron loss increases.
Furthermore, sample no. In the example No. 28, the B content exceeds the upper limit of 14.0 atomic%, and the C content exceeds the upper limit of 4.0 atomic%, and the iron loss increases; 29 is an example in which the Si content is 6.0 atomic% or less as the lower limit, and the C content exceeds the upper limit 4.0 atomic% and the iron loss is increased.

  From these comparisons, it was found that according to the present invention, it is possible to realize an excellent iron loss such that the iron loss at a magnetic flux density of 1.3 T and the frequency of 50 Hz is 0.085 W / kg or less in the Fe-based amorphous alloy.

(Example 2)
Table 1 No. With respect to the alloy shown in 6, using various types of alloys in which part of Fe was replaced with at least one or more of Ni, Cr, and Co, a ribbon was produced using the same apparatus and conditions as in Example 1. The specific components of the used alloy are shown in Table 2 only for Ni, Cr and Co. As a result, the thickness, width and length of the obtained ribbon were about 25 μm, 20 mm and about 50 m, respectively. It evaluated about the saturation magnetic flux density and core loss of the obtained thin strip. The sample collection method and measurement conditions used for these characterizations were the same as in Example 1. The measurement results are shown in Table 2. In addition, the display point in Table 2 is the same as that of the case of Table 1.

Sample No. in Table 2 As is apparent from the results of 30 to 36, even if at least one of Ni, Cr and Co is substituted for at least one of Ni, Cr and Co in a range of 10.0 atomic% or less, the iron loss W _13/50 is stable It was then found to be 0.085 W / kg or less. Also, for sample no. 30 to 36 had a saturation magnetic flux density of 1.5 T or more. Furthermore, sample no. No clear diffraction peak was observed in the X-ray diffractometer, and it was confirmed that 30 to 36 were amorphous.

(Example 3)
Table 1 No. For the alloy shown in No. 17, a thin strip was manufactured using the same apparatus and conditions as in Example 1, using an alloy of various components in which a part of Fe was replaced with at least one of Ni, Cr and Co. In addition, about the specific component of the used alloy, Table 3 showed only Ni, Cr, and Co. As a result, the thickness, width and length of the obtained ribbon were respectively about 25 μm, 20 mm and about 50 m. It evaluated about the saturation magnetic flux density and core loss of the obtained thin strip. The sample collection method and measurement conditions used for these characterizations were the same as in Example 1. The measurement results are shown in Table 3. In addition, the display point in Table 3 is the same as that of the case of Table 1.

The sample numbers in Table 3 As is apparent from the results of 37 to 43, even if a part of Fe is replaced with at least one or more of Ni, Cr and Co in the range of 10 atomic% or less, the iron loss W _13/50 is stable It turned out that it becomes below 0.085 W / kg. Also, for sample no. 37 to 43 had a saturation magnetic flux density of 1.5 T or more. Furthermore, sample no. No clear diffraction peak was observed in X-ray diffraction measurement, and 37 to 43 were confirmed to be amorphous.

  According to the present invention, it has become possible to stably manufacture, on an industrial scale, a Fe-based amorphous alloy having a lower iron loss, that is, a good quality, for example, a Fe-based amorphous alloy ribbon. Since the characteristics of the Fe-based amorphous alloy of the present invention are better in quality than conventional Fe-based amorphous alloys, industrial applicability is high.

Claims (5)

  At atomic%, B is 10.0% or more and 14.0% or less, Si is more than 6.0% and 8.0% or less, C is more than 1.0% and 4.0% or less, and the balance is Fe and unavoidable impurities Fe-based amorphous alloy characterized by comprising:   In atomic%, B is 10.0% or more and 14.0% or less, Si is more than 6.0% and 8.0% or less, C is more than 1.0% and 4.0% or less, and B, Si, Fe-based amorphous characterized in that the total content of C is 17.0% or more and 19.0% or less, or 23.0% or more and 25.0% or less, with the balance being Fe and unavoidable impurities. alloy.   Fe is characterized in that Fe of the Fe-based amorphous alloy according to claim 1 or claim 2 is substituted with at least one or more of Ni, Cr and Co in a range of 10.0 atomic% or less Amorphous alloy. The magnetic flux density 1.3 T, Fe system according to any one of claims 1 to 3, iron loss at a frequency 50 Hz (iron loss _{W 13/50)} is equal to or less than 0.085W / kg Amorphous alloy. An Fe-based amorphous alloy ribbon comprising the Fe-based amorphous alloy according to any one of claims 1 to 4.