JP2018123424A - Fe-BASED AMORPHOUS ALLOY AND Fe-BASED AMORPHOUS ALLOY THIN STRIP HAVING EXCELLENT SOFT MAGNETIC PROPERTIES - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an Fe-based amorphous alloy and an Fe-based amorphous alloy thin strip that achieve reduced iron loss while maintaining a high magnetic flux density.SOLUTION: The present invention provides an Fe-based amorphous alloy and an Fe-based amorphous alloy thin strip having excellent soft magnetic properties, containing, in atom%, Fe of 76.00% or more, B of 10.0% or more and 14.0% or less, Si of 4.0% or more and 8.0% or less, C of 1.0% or more and 4.0% or less, Mn of 0.05% or more and 2.00% or less, Mo of 0.005% or more and 3.000% or less, with the balance being inevitable impurities.SELECTED DRAWING: None

Description

  The present invention relates to an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon used for iron cores such as power transformers and high-frequency transformers.

  Centrifugal quenching method, single roll method, twin roll method and the like are known as methods for continuously producing ribbons and wires by rapidly cooling an alloy from a molten state. In these methods, molten metal is ejected from an orifice or the like to the inner or outer peripheral surface of a metal drum that rotates at high speed, whereby the molten metal is rapidly solidified to produce a ribbon or wire. Further, by appropriately selecting the alloy composition, an amorphous alloy similar to a liquid metal can be obtained, and a material excellent in 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 is 60 to 90% in atomic percent, and at least one of P, C, and B is 10 to 30%, Al, Si. , Sn, Sb, Ge, In, Be, and at least one alloy component of 0.1 to 15% has been proposed. The technology described in Patent Document 1 proposes an alloy component that can obtain an amorphous phase, and proposes a component that focuses only on the so-called magnetic properties, especially for applications such as power cores and high frequency transformers. is not.

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

  Among the amorphous alloy components proposed in Patent Documents 1 and 3, the iron loss as energy loss is low, the saturation magnetic flux density and the magnetic permeability are high, and an amorphous phase can be obtained stably. For these reasons, for example, an FeSiB-based amorphous alloy as shown in Patent Document 2 has come to be promising as an application for an iron core of a power transformer or a high-frequency transformer.

  Since then, development related to alloy components of Fe-based amorphous alloys with excellent soft magnetic properties has been proceeding with a focus on this FeSiB system. That is, development of further reduction of iron loss in FeSiB-based amorphous alloys has been actively conducted, and many results have been produced.

For example, Patent Documents 4 and 5 show that iron loss W _13/50 by single plate measurement (iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz) is stable. To a low iron loss of 0.10 W / kg or less.

  That is, the present inventors disclosed in Patent Document 4 that, for example, in atomic percent, Fe is 70% to 86%, B is 7% to 20%, Si is 1% to 19%, and C is 4% or less. An alloy component containing the balance and inevitable impurities was proposed.

  On the other hand, in the patent document 5, the present inventors include, for example, atomic%, B is 7% to 20%, Si is 1% to 19%, C is 0.02% to 4%, and the balance An alloy component consisting of Fe and inevitable impurities was proposed.

  Furthermore, the present inventors disclosed in Patent Document 6 that, for example, in atomic percent, Fe is 80% to 82%, B is 12% to 16%, Si is 2% to 7%, and C is 0.003. The alloy component which consists of 2% or less and 2% or less and which consists of the balance inevitable impurities was proposed.

  Thereafter, proposals as shown in Patent Documents 7 and 8 were also made. That is, in Patent Document 7, for example, in 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%. An alloy component containing 0.001% or more and 5% or less and the balance of inevitable impurities was proposed.

  On the other hand, Patent Document 8 contains, for example, atomic%, Fe of 76% to 84%, B of 8% to 18%, Si of 12% or less, and C of 0.01% to 3%. An alloy ribbon is proposed which is composed of the remaining inevitable impurities and has a C segregation layer in the depth direction of 2 to 20 nm from the surface of the free and roll surfaces.

In Patent Document 9, Fe is 80% to 88%, P is 6% to 16%, C is 2% to 8%, Al is 0.1% to 3% in atomic%, the Mo containing less than 5% 0.1%, the balance being unavoidable impurities, the iron loss _{W 13/50,} and proposed an amorphous alloy below 0.10 W / kg.

In Patent Document 10, Fe is 80% to 88%, P is 4% to 12%, B is 2% to 8%, and Al is 0.1% to 3% in atomic%. further, a Mo containing 6% or less than 0.1%, the balance being unavoidable impurities, the iron loss _{W 13/50,} and proposed an amorphous alloy below 0.10 W / kg.

JP-A-49-91014 JP 57-116750 A JP 61-30649 A JP-A-8-283920 JP-A-9-95760 JP 2006-31777 A JP 2006-045660 A JP 2006-045662 A JP 2006-117929 A JP, 2006-151055, A

  However, development of iron loss reduction in amorphous alloys has been considerably progressed so far, but further improvement of iron loss is strongly demanded. This is because the problem of improving energy loss with electric power is a very pressing issue.

  An object of the present invention is to respond to such needs for further reduction in iron loss, Fe-based amorphous alloy and Fe-based amorphous alloy capable of realizing further reduction in iron loss while maintaining a high magnetic flux density. To provide a ribbon.

The present inventor, among the constituent elements of various alloy components that have been proposed so far, is a component system in which, for example, Fe described in Patent Documents 4 and 5 is mainly used, and B, Si, and C are alloy elements. In order to maintain the high magnetic flux density, further investigations and experiments were conducted to further reduce the iron loss. And, as a result of conducting detailed experiments based on a component system mainly composed of Fe and mainly containing B, Si, and C, and further combining other elements, a saturation magnetic flux density of 1.50 T or more is maintained. , iron loss (core loss _{W 13/50)} was found component range of the amorphous alloy to be less stable and 0.085W / kg. And based on this knowledge, examination was repeated and it came to complete this invention.

This invention is made | formed based on the said knowledge, The summary is as follows.
(1) In the present invention, Fe is 76.00% or more, B is 10.0% or more and 14.0% or less, Si is 4.0% or more and 8.0% or less, and C is 1.0%. % To 4.0%, Mn from 0.05% to 2.00%, Mo from 0.005% to 3.000%, and the balance consisting of inevitable impurities The present invention relates to an Fe-based amorphous alloy having excellent characteristics.
(2) In the present invention, Fe is 76.00% or more, B is 10.0% or more and 14.0% or less, Si is 4.0% or more and 8.0% or less, and C is 1.0%. % To 4.0%, Mn from 0.05% to 2.00%, Mo from 0.005% to 3.000%, and the total of B, Si, C, Mn, and Mo The present invention relates to an Fe-based amorphous alloy having excellent soft magnetic characteristics, characterized in that the content is 18.20% or more and 22.50% or less, and the balance is inevitable impurities.
(3) In the present invention, at least one of Ni, Cr, and Co is used, and Fe in the Fe-based amorphous alloy according to (1) or (2) is substituted within a range of 10.0 atomic% or less. The present invention relates to an Fe-based amorphous alloy having excellent soft magnetic characteristics.
(4) The present invention, the magnetic flux density 1.3 T, the iron loss at a frequency 50 Hz (iron loss _{W 13/50)} is 0.085W / kg or less, and said the saturation magnetic flux density is not less than 1.50T The present invention relates to an Fe-based amorphous alloy having excellent soft magnetic properties according to any one of (1) to (3).
(5) The present invention relates to a Fe-based amorphous alloy ribbon excellent in soft magnetic properties, characterized by comprising the Fe-based amorphous alloy according to any one of (1) to (4). .

According to the present invention, while the saturation magnetic flux density was maintained above 1.50T, a stable iron loss (iron loss _{W 13/50),} Fe-based amorphous which can be below 0.085W / kg Alloy and Fe-based amorphous alloy ribbon can be provided.

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 this embodiment is that the Fe, B, Si, C alloy has a component range in which the iron loss is extremely low by optimizing the content of these constituent elements, and is further optimal. by including an amount of Mn and Mo, the iron loss (iron loss _{W 13/50)} is in fact it was realized to be a less stable 0.085W / kg. In addition, the Fe-based amorphous alloy of the present embodiment lies in that soft magnetic characteristics are further improved by substituting part of Fe as a base with Ni, Cr, and Co. The iron loss W _13/50 here is an iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz in the measurement of iron loss with a single plate.

Moreover, the iron loss W _13/50 is measured as follows. The molten alloy is rapidly solidified to produce an amorphous alloy ribbon. Samples for measuring iron loss W _13/50 are taken from a plurality of measurement points over the entire length of the obtained amorphous alloy ribbon. The iron loss W _13/50 is measured for each sample, and the maximum value among them is defined as the iron loss W _13/50 . The number of measurement locations is not particularly limited, but may be, for example, 6 locations or more. The iron loss W _13/50 of the amorphous alloy ribbon varies somewhat, but in this embodiment, since the maximum value is 0.085 W / kg or less, the Fe-based non-ferrous iron having a stable and low iron loss. A crystalline alloy can be obtained. More preferably the iron loss _{W 13/50} or less 0.083W / kg, more preferably not more than 0.080W / kg.

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

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

In other words, in order to achieve further reduction in iron loss based on, for example, Patent Documents 4 and 5, the present inventor details the relationship between the contents of Mn and Mo and iron loss in addition to B, Si, and C. Examination, in the area of optimizing the combination of the content of these elements was found that iron loss _{W 13/50} becomes less stable 0.085W / kg.

  Therefore, in the present invention, the contents of B, Si, C, Mn, and Mo are limited as follows. That is, in atomic%, B is 10.0% to 14.0%, Si is 4.0% to 8.0%, C is 1.0% to 4.0%, and Mn is 0.05. % And 2.00% or less, and further Mo is limited to 0.005% or more and 3.000% or less.

Furthermore, B, Si, C, Mn, the total content of Mo With 22.50% less than 18.20%, the iron loss _{W 13/50} becomes less stable 0.083W / kg Is also possible.

On the other hand, at least one element of B, Si, C, Mn, and Mo is atomic%, B is less than 10.0% or more than 14.0%, and Si is less than 4.0% or 8.0. %, C is less than 1.0% or more than 4.0%, Mn is less than 0.05% and more than 2.00%, and Mo is less than 0.005% and more than 3.000%, the iron loss W _{13 /} It is difficult to stabilize ₅₀ to 0.085 W / kg or less.

  In an Fe-based amorphous alloy, a practical level of saturation magnetic flux density is generally obtained when the Fe content is 70 atomic% or more, but in order to obtain a high saturation magnetic flux density of 1.50 T or more. For this, Fe needs to be 76.00 atomic% or more. Therefore, in the Fe-based amorphous alloy of this embodiment, the Fe content is limited to a range of 76.00 atomic% or more. In addition, it is preferable that the upper limit of Fe content shall be 86.00 atomic% or less. This is because if the Fe content exceeds 86.00 atomic%, it is difficult to form an amorphous phase.

  In the Fe-based amorphous alloy of this embodiment, a part of Fe is replaced with at least one of Ni, Cr, and Co in a range of 10.0 atomic% or less, and a high saturation magnetic flux density is maintained. Improvements in soft magnetic properties such as iron loss can also be realized. The reason for setting an upper limit for the amount of substitution by these elements is that if it exceeds 10.0 atomic%, the saturation magnetic flux density is lowered and the raw material cost is increased.

  The balance of the Fe-based amorphous alloy of this embodiment is an inevitable impurity. Inevitable impurities are permissible as long as the effects of the present invention are not impaired.

  The Fe-based amorphous alloy of this embodiment can be usually obtained in the form of a ribbon. This Fe-based amorphous alloy ribbon melts the alloy composed of the components described in the above embodiment, and ejects the molten metal onto a cooling plate moving at high speed via a slot nozzle or the like. It can be produced by a rapid solidification method such as a single roll method or a twin roll method. The roll used in these roll methods is made of metal, and the alloy can be rapidly solidified by rotating the roll at high speed and causing the molten metal to collide with the roll surface or the roll inner surface.

  The single roll device includes a centrifugal quenching device that uses the inner wall of the drum, a device that uses an endless belt, and an improved version of these auxiliary rolls and roll surface temperature control devices. Also included are casting devices in or in an inert gas.

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

Note that the Fe-based amorphous alloy of the present embodiment can be powdered in addition to the ribbon. In that case, a method of rapidly cooling and solidifying the molten alloy or droplets of molten alloy in a liquid such as a rotating roll or cooling water from a crucible nozzle filled with the molten alloy of the above composition is adopted. can do.
By the above-mentioned method, an Fe-based amorphous alloy powder can be obtained.

  The Fe-based amorphous alloy powder thus obtained is compacted by a mold or the like and formed into a desired shape, and is sintered and integrated as necessary, so that a power transformer, a high-frequency transformer, a coil It can be applied as a use of iron cores.

  Whether or not the Fe-based amorphous alloy of the present embodiment has an amorphous structure can be confirmed by, for example, X-ray diffraction measurement using an X-ray diffractometer using an Fe tube. That is, when a clear diffraction peak is not obtained in the 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
Alloys of various components shown in Table 1 below were dissolved in an argon atmosphere and cast with a single roll device to produce a ribbon. The casting atmosphere was in the air. And the soft magnetic characteristic was investigated about the obtained thin strip. The single roll apparatus used is composed of a copper alloy cooling roll having a diameter of 300 mm, a high frequency power source for sample dissolution, a quartz crucible with a slot nozzle at the tip, and the like.

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

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

Sample No. in Table 1 As is clear from the results of 1 to 18, Fe is 76.00 atomic% or more, B is 10.0 atomic% or more and 14.0 atomic% or less, Si is 4.0 atomic% or more and 8.0 atomic% or less, By making C within the range of 1.0 atomic% to 4.0 atomic%, Mn from 0.05 atomic% to 2.00 atomic%, and Mo from 0.005% to 3.000%. An Fe-based amorphous alloy ribbon having good soft magnetic properties, with a magnetic flux density of 1.3 T and a core loss at a frequency of 50 Hz of 0.085 W / kg or less, while maintaining a saturation magnetic flux density of 1.50 T or more is obtained. I found out that On the other hand, sample No. 1-No. 7, no. 10-No. 14, no. As apparent from the result of 16, the iron loss W _13/50 is stabilized by setting the total content of B, Si, C, Mn, and Mo to 18.20 atomic% or more and 22.50 atomic% or less. It was found that an Fe-based amorphous alloy ribbon having better soft magnetic properties of 0.083 W / kg or less can be obtained. Sample No. 1 to 18 were confirmed to be amorphous, with no clear diffraction peak observed in the X-ray diffraction measurement.

In contrast, sample no. In the comparative examples shown in 19 to 29, although the ribbon was obtained, the characteristics satisfying both the saturation magnetic flux density of 1.50 T or more and the iron loss of 0.085 W / kg or less were not obtained.

Sample No. No. 19 is an example in which the Fe content is below the lower limit of 76.00 atomic%, the saturation magnetic flux density is decreased, and the iron loss is increased. No. 20 is an example in which the iron content increased beyond the upper limit of 14.0 atomic% of the desirable B content. No. 21 is an example in which the iron loss increased below the lower limit of 10.0 atomic% of the desirable range of B content. No. 22 is an example in which the iron loss increased below the lower limit of 4.0 atomic% in the range where the Si content is desirable. No. 23 is an example in which the Si content exceeded the upper limit of 8.0 atomic% and the iron loss increased.
Sample No. No. 24 is an example in which the C content was below the lower limit of 1.0 atomic% and the iron loss increased. 25 is an example in which the C content exceeded the upper limit of 4.0 atomic% and the iron loss increased.
Sample No. No. 26 is an example in which the iron loss increased below the lower limit of 0.05 atomic% of the desirable range of Mn content. No. 27 is an example in which the iron loss is increased by exceeding the upper limit of 2.00 atomic% of the desirable range of Mn content.
Sample No. No. 28 is an example in which the iron loss increased below the lower limit of 0.005 atomic% of the desired Mo content. No. 29 is an example in which the iron loss is increased by exceeding the upper limit of 3.000 atomic% of the desired Mo content.

  From these contrasts, according to the present invention, the Fe-based amorphous alloy has an excellent iron loss of 0.085 W / kg or less at a magnetic flux density of 1.3 T and a frequency of 50 Hz while maintaining a high saturation magnetic flux density of 1.50 T or more. It was found that the iron loss can be realized.

(Example 2)
No. in Table 1 About the alloy shown in No. 1, a ribbon was produced under the same apparatus and conditions as in Example 1 using alloys of various components in which part of Fe was replaced with at least one of Ni, Cr, and Co. In addition, about the specific component of the used alloy, only Ni, Cr, Co was shown in Table 2. As a result, the thickness, width, and length of the obtained ribbon were about 25 μm, 20 mm, and about 50 m, respectively. The obtained thin strip was evaluated for saturation magnetic flux density and iron loss. The sample collection method and measurement conditions used for these characteristic evaluations were the same as those in Example 1. The measurement results are shown in Table 2. The display procedure in Table 2 is the same as that in Table 1.

Sample No. in Table 2 As is clear from the results of 30 to 36, even when a part of Fe is replaced with at least one of Ni, Cr, and Co in a range of 10.0 atomic% or less, the saturation magnetic flux density becomes 1.50 T or more. , iron loss _{W 13/50} were found to be less stable and 0.085W / kg.
Sample No. 30 to 36 were confirmed to be amorphous, with no clear diffraction peak observed in the X-ray diffraction measurement.

(Example 3)
No. in Table 1 For the alloy shown in Fig. 7, a ribbon was produced using the same apparatus and conditions as in Example 1 using alloys 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, only Ni, Cr, and Co was shown in Table 3. As a result, the thickness, width, and length of the obtained ribbon were about 25 μm, 20 mm, and about 50 m, respectively. The obtained thin strip was evaluated for saturation magnetic flux density and iron loss. The sample collection method and measurement conditions used for these characteristic evaluations were the same as those in Example 1. The measurement results are shown in Table 3. The display procedure in Table 3 is the same as that in Table 1.

Sample No. in Table 3 As is apparent from the results of 37 to 43, even when a part of Fe is replaced with at least one of Ni, Cr, and Co in the range of 10 atomic% or less, the saturation magnetic flux density is 1.50 T or more, and iron loss _{W 13/50} was found to be less stable and 0.085W / kg.
Sample No. No clear diffraction peak was observed in X-ray diffraction measurement, and it was confirmed that 37 to 43 were amorphous.

  According to the present invention, it is possible to stably produce an Fe-based amorphous alloy, for example, a Fe-based amorphous alloy ribbon, on an industrial scale, having a lower iron loss while maintaining a high saturation magnetic flux density, that is, good quality. Became possible. Since the characteristics of the Fe-based amorphous alloy of the present invention are better than those of conventional Fe-based amorphous alloys, the industrial applicability is great.

Claims (5)

  Atomic%, Fe is 76.00% or more, B is 10.0% or more and 14.0% or less, Si is 4.0% or more and 8.0% or less, and C is 1.0% or more and 4.0% or less. Fe-based non-magnetic material having excellent soft magnetic characteristics, characterized by containing Mn 0.05% or more and 2.00% or less, Mo 0.005% or more and 3.000% or less, and the balance being inevitable impurities A crystalline alloy.   Atomic%, Fe is 76.00% or more, B is 10.0% or more and 14.0% or less, Si is 4.0% or more and 8.0% or less, and C is 1.0% or more and 4.0% or less. , Mn is 0.05% or more and 2.00% or less, Mo is 0.005% or more and 3.000% or less, and the total content of B, Si, C, Mn and Mo is 18.20%. An Fe-based amorphous alloy excellent in soft magnetic characteristics, characterized in that the content is 22.50% or less and the balance is inevitable impurities.   A soft material characterized by substituting at least one of Ni, Cr and Co for Fe in the Fe-based amorphous alloy according to claim 1 or 2 within a range of 10.0 atomic% or less. Fe-based amorphous alloy with excellent magnetic properties. Magnetic flux density 1.3 T, the iron loss at a frequency 50Hz is (iron loss _{W 13/50)} 0.085W / kg or less, and claims 1, wherein the saturation magnetic flux density is not less than 1.50T 4. An Fe-based amorphous alloy having excellent soft magnetic properties according to any one of 3 above.   An Fe-based amorphous alloy ribbon excellent in soft magnetic properties, comprising the Fe-based amorphous alloy according to any one of claims 1 to 4.