JP5320764B2 - Fe-based amorphous alloy with excellent soft magnetic properties - Google Patents

Description

  The present invention relates to a 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. This patent proposes an alloy component capable of obtaining an amorphous phase, and is not a proposal of a component focusing on only so-called magnetic properties, particularly limited to uses such as iron cores such as power transformers and high-frequency transformers.

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%, at least one of B, C and P is 10 to 30%, and the content of Fe and Co is Ni. Up to 3/4, V, Cr, Mn, Mo, Nb, Ta, W can be substituted up to 1/4, and B, C, P content can be up to 3/5 for Si, Al for Al Alloy components that can be substituted for up to 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.

However, although the development of iron loss reduction in amorphous alloys has progressed considerably, the demand for improvement in characteristics in this application is still strong, and further improvement in iron loss is required. For example, the iron loss W13 / 50 (magnetic loss 1.3T, iron loss at a frequency of 50 Hz) measured by a single plate with respect to the iron loss can be improved to below 0.12 W / kg. It was very difficult to stably achieve 0.10 W / kg or less.
JP-A-49-91014 JP 57-116750 A JP 61-30649 A

  An object of the present invention is to provide an amorphous alloy that can realize further reduction in iron loss in order to meet the need for further improvement in iron loss.

  The inventor of the present invention pays attention to the elements of P, C, and B classified as the second component group in Patent Documents 1 and 3 described above, for example, among the constituent elements of various alloy components that have been proposed so far. Then, the combination and content of these elements were examined and experimented again. As a result of detailed experiments combining other elements based on the component system mainly composed of P and B, the problem can be realized, that is, iron loss W13 / 50 (magnetic flux density 1.3T, frequency 50Hz). In other words, the present inventors have found an amorphous alloy component that can stably realize 0.10 W / kg or less in terms of iron loss. And based on this knowledge, examination was repeated and it came to complete this invention.

The present invention is as follows.
(1) Atomic%, Fe is 78% to 86%, P is 8% to 20%, B is 1% to 12% , and Si is 0.1% to 1.7 %. And an Fe-based amorphous alloy having excellent soft magnetic characteristics, comprising 0.1% to 1.9% of Al and the balance being inevitable impurities.
(2) Fe-based non-excellent soft magnetic properties characterized by substituting at least one of Ni, Cr and Co for Fe in the alloy described in (1) in a range of 30% or less. A crystalline alloy.
(3) Atomic%, Fe is 78% to 86%, P is 8% to 20%, B is 1% to 12% , and Si is 0.1% to 1.7 %. A Fe-based amorphous alloy having excellent soft magnetic characteristics, comprising 0.005% or more and 1.9% or less of Al and the balance being inevitable impurities.
(4) Fe-based non-excellent soft magnetic characteristics characterized in that at least one of Ni, Cr, and Co is substituted for Fe in the alloy described in (3) within a range of 30% or less. A crystalline alloy.

  According to the present invention, the iron loss of the amorphous alloy can be further reduced, and the iron loss W13 / 50 by the single plate measurement can be stably reduced to 0.10 W / kg or less. Furthermore, since the content of B can be reduced as compared with the conventional alloy, the manufacturing cost can be reduced.

Hereinafter, the present invention will be described in detail.
A feature of the present invention is that, in an alloy based on Fe, P and B are added, and Si and Al are selectively added to optimize the type and content of the constituent elements. In particular, it has been achieved that iron loss can be stably lowered in a lot. Another advantage is that the soft magnetic properties are further improved by replacing part of the base Fe with Ni, Cr, and Co.

  First, the reason for limiting the content of each element will be described. P and B are added to improve the amorphous phase formation and the thermal stability of the amorphous phase. Furthermore, it is possible to further improve the iron loss value by optimizing the content of these elements. For example, the iron loss W13 / 50 by the single plate measurement can be stably reduced to 0.10 W / kg or less. it can. If P is less than 8 atomic% and B is less than 1 atomic%, an amorphous alloy cannot be stably obtained, so it is difficult to stably reduce the iron loss to 0.10 W / kg or less. On the other hand, even if P is more than 20 atomic% and B is more than 12 atomic%, an amorphous phase cannot be obtained stably, and iron loss can be stably reduced to 0.1 W / kg or less at W13 / 50. become unable. Therefore, P is limited to the range of 8 atomic% to 20 atomic% and B is limited to the range of 1 atomic% to 12 atomic%. In particular, from the viewpoint of good iron loss and manufacturing cost reduction, it is more preferable that P is 10 atomic% to 18 atomic% and B is 1 atomic% to 8 atomic%.

Further, when Si and Al are added, the amorphous phase forming ability is improved, and the thermal stability of the amorphous phase is further improved. These elements Dochi et al. Also effective to add both simultaneously. The contents of Si are 0.1 atomic% or more and 1.7 atomic% or less, and Al is 0.005 atomic% or more and 1.9 atomic% or less. In the case of Si, if less than 0.1 atomic%, the effect is not recognized, and if it exceeds 1.7 atomic%, this effect is no longer effective. On the other hand, in the case of Al, if less than 0.005 atomic%, the effect is not recognized, and if it exceeds 1.9 atomic%, this effect is not recognized so much .

  When the Fe content is usually 70 atomic% or more, a practical level of saturation magnetic flux density as a general iron core can be obtained, but in order to obtain a high saturation magnetic flux density of 1.5 T or more, Fe is used. It needs to be 78 atomic% or more. On the other hand, when the Fe content exceeds 86 atomic%, it becomes difficult to form an amorphous phase, and it becomes difficult to stably reduce the iron loss W13 / 50 to 0.10 W / kg or less. Therefore, the Fe content is limited to a range of 78 atomic% to 86 atomic%.

  In the present invention, by replacing a part of Fe with at least one of Ni, Cr, and Co in the range of more than 0 and 30 atomic% or less, improvement of soft magnetic properties such as magnetic permeability and magnetic flux density can be realized, Moreover, the iron loss can be stably reduced to 0.10 W / kg or less at W13 / 50. The reason why the substitution amount by these elements is limited is that the raw material cost increases when it exceeds 30 atomic%.

  A thin ribbon of the amorphous alloy of the present invention is a method of melting the alloy comprising the components of the present invention, spraying the molten metal on a cooling plate moving at high speed through a slot nozzle or the like, and rapidly solidifying the molten metal, For example, it can be produced by a single roll method or a twin roll method. The single roll device is equipped with a centrifugal quenching device that uses the inner wall of the drum, a device that uses an endless belt, and an auxiliary roll or a roll surface temperature control device that is an improved version of these devices. A casting apparatus under reduced pressure or in a vacuum or in an inert gas is also included. In the present invention, the thickness and width of the ribbon are not particularly limited, but the thickness of the ribbon is preferably 10 μm or more and 100 μm or less, for example. The plate width is preferably 10 mm or more.

Examples of the present invention will be further described below.
Example 1
Alloys of various components shown in Table 1 were melted in an argon atmosphere and cast into a thin strip by a single roll method. The casting atmosphere was in the air. And the ribbon property was investigated about the obtained ribbon. The single roll ribbon manufacturing 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, and the plate width was 20 mm because it depends on the length of the slot nozzle.

  The iron loss of the ribbon was performed using SST (Single Strip Tester). The measurement conditions are a magnetic flux density of 1.3 T and a frequency of 50 kHz. For the iron loss measurement sample, strip samples cut from 12 locations to 120 mm length over the entire length of one lot were used, and the strip samples were annealed at 360 ° C. for 1 hour in a magnetic field. It used for the measurement. The atmosphere in the anneal was nitrogen.

  Table 1 shows the maximum value (Wmax), the minimum value (Wmin), and the deviation ((Wmax−Wmin) / Wmin) in one lot as iron loss measurement results.

Sample No. in Table 1 24 As is apparent from the results of to 32, Fe 78 at% or more 86 atomic% or less, 8 atomic% to 20 atomic% or less P, B 1 atomic% or more and 12 atomic% or less, a Si 0.1% By making the range of the present invention 1.7 % or less and Al 0.005% or more and 1.9% or less, the iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz is less than 0.1 W / kg, and The deviation ((Wmax−Wmin) / Wmin) was less than 0.1, and it was found that a ribbon having excellent soft magnetic properties was obtained over the entire length of the ribbon.
In contrast, sample no. In the component range of the comparative example shown in 33 to 42, there is a portion where the iron loss is greater than 0.1 W / kg, and the deviation ((Wmax−Wmin) / Wmin) is also 0.1 or more.
From these times, it was found that the present invention can realize further improvement of soft magnetic properties.

(Example 3 )
No. in Table 1 As for the alloy shown in FIG. 25, a ribbon was cast under 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 of the obtained ribbon was about 25 μm. The iron loss of the obtained ribbon was evaluated. The method for collecting the measurement sample and the measurement conditions for the iron loss evaluation were the same as 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 clear from the results of 1 to 7, even if a part of Fe is replaced with at least one of Ni, Cr, and Co in the range of 30 atomic% or less, the iron loss is stably reduced to W13 / 50. It was found that it could be less than 10 W / kg.

(Example 4 )
No. in Table 1 With respect to the alloy shown in FIG. 31, a ribbon was cast using 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, and Co was shown in Table 5. As a result, the thickness of the obtained ribbon was about 25 μm. The iron loss of the obtained ribbon was evaluated. The method for collecting the measurement sample and the measurement conditions for the iron loss evaluation were the same as in Example 1. The measurement results are shown in Table 4 . The display procedure in Table 4 is the same as that in Table 1.

Sample No. in Table 4 As is clear from the results of 1 to 7, even if a part of Fe is replaced with at least one of Ni, Cr, and Co in the range of 30 atomic% or less, the iron loss is stably reduced to W13 / 50. It was found that it could be less than 10 W / kg.

  The alloy of the present invention can be widely used as a soft magnetic material used for iron cores of power transformers and high-frequency transformers, as well as parts of various electromagnetic devices and magnetic shield materials.

Claims (4)

Atomic%, Fe is 78% to 86%, P is 8% to 20%, B is 1% to 12% , Si is 0.1% to 1.7 % and Al is contained. An Fe-based amorphous alloy excellent in soft magnetic characteristics, characterized by containing 0.1% or more and 1.9% or less and the balance being inevitable impurities.   An Fe-based amorphous alloy having excellent soft magnetic characteristics, wherein at least one of Ni, Cr and Co is substituted for Fe in the alloy according to claim 1 in a range of 30% or less. Atomic%, Fe is 78% to 86%, P is 8% to 20%, B is 1% to 12% , Si is 0.1% to 1.7 % and Al is contained. An Fe-based amorphous alloy having excellent soft magnetic characteristics, characterized by containing 0.005% or more and 1.9% or less and the balance being inevitable impurities.   An Fe-based amorphous alloy having excellent soft magnetic characteristics, wherein at least one of Ni, Cr and Co is substituted for Fe in the alloy according to claim 3 in a range of 30% or less.