JP6601139B2 - Fe-based amorphous alloy and Fe-based amorphous alloy ribbon with excellent soft magnetic properties - Google Patents

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 technique described in Patent Document 1 proposes an alloy component that can obtain an amorphous phase, and proposes a component that focuses on only the so-called magnetic properties, especially for applications such as power cores and high-frequency transformer cores. 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%, 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.

  The improvement of the iron loss in the amorphous alloy is considerably advanced. For example, according to Patent Document 4, the iron loss W13 / 50 (iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz) measured by a single plate is stably reduced to 0. It came to be able to implement | achieve the low iron loss of 100 W / kg or less.

  That is, in Patent Document 4, Fe is 78% to 86%, B is 8% to 18%, C is 3% to 10%, Si is 0.1% to 5% in atomic%, An alloy component containing 0.1% or more and 3% or less of Al with the remainder unavoidable impurities has been proposed.

JP-A-49-91014 JP 57-116750 A JP 61-30649 A JP 2008-240147 A

  Conventionally, development of iron loss reduction in amorphous alloys has progressed considerably, but on the other hand, there is a strong demand for improvement in magnetic flux density in applications such as iron cores such as power transformers and high-frequency transformers. However, conventionally, it has been very difficult to obtain an amorphous alloy in which the saturation magnetic flux density is stably 1.60 T or more while maintaining a low iron loss.

  The present invention provides an Fe-based amorphous alloy and an Fe-based amorphous alloy ribbon that can realize a higher magnetic flux density while maintaining a low iron loss in order to meet such needs for magnetic flux density improvement. Let it be an issue.

  The present inventor pays attention to the component system composed of B, C, Si, and Al mainly composed of Fe described in, for example, Patent Document 4 among the constituent elements of various alloy components proposed so far. Then, investigation and experiment were carried out to further increase the magnetic flux density while maintaining low iron loss. Further, as a result of detailed experiments based on a component system mainly composed of Fe and additive elements mainly including B, C, Si, and Al and further combined with other elements, the saturation magnetic flux density is stabilized. A component of an amorphous alloy that is 60 T or more was found. 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) Atomic%, Fe is 80.0% or more and 88.0% or less, B is 6.0% or more and 12.0% or less, C is 2.0% or more and 8.0% or less, and Si is 0.00. 10% or more and 3.0% or less, the Al containing 2.0% to 0.10%, further, a Mo containing 6.0% or less 0.10% or more, Ri Do the balance incidental impurities, the magnetic flux density 1.3 T, the iron loss at a frequency 50Hz (W13 / 50) is 0.100W / kg or less, and, Fe-based non-saturation magnetic flux density and excellent soft magnetic properties, characterized in der Rukoto than 1.60T A crystalline alloy.
(2) Excellent soft magnetic characteristics, characterized by substituting at least one of Ni, Cr and Co for Fe of the alloy described in (1) in a range of 10.0 atomic% or less. Fe-based amorphous alloy.
( 3 ) An Fe-based amorphous alloy ribbon comprising the Fe-based amorphous alloy according to (1) or (2) .

According to the present invention, it is possible to provide an Fe-based amorphous alloy having a saturation magnetic flux density of 1.60 T or more while maintaining a low iron loss.
Further, according to the present invention, it is possible to provide an Fe-based amorphous alloy ribbon having a saturation magnetic flux density of 1.60 T or more while maintaining a low iron loss.

Hereinafter, the Fe-based amorphous alloy according to the embodiment of the present invention will be described in detail.
The feature of the Fe-based amorphous alloy of this embodiment is that, by adding Mo to the alloy composed of Fe, B, C, Si, and Al and optimizing the content of the constituent elements, soft magnetic properties, In particular, it has been achieved that the saturation magnetic flux density is stably increased in the production lot while maintaining a low iron loss. In addition, the Fe-based amorphous alloy of the present embodiment lies in that soft magnetic characteristics are further improved by substituting a part of the base Fe with Ni, Cr, and Co. The low iron loss is an iron loss W13 / 50 (iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz) measured by a single plate, and stably indicates 0.100 W / kg or less. In this embodiment, An Fe-based amorphous alloy exhibiting a high saturation magnetic flux density of 1.60 T or more can be realized with this low iron loss characteristic.

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

  B and C are added to improve the formation of the amorphous phase and the thermal stability of the amorphous phase in the Fe-based amorphous alloy of this embodiment. Furthermore, by optimizing the content of these elements, it is possible to further improve the soft magnetic characteristics. For example, it is possible to stably achieve a saturation magnetic flux density of 1.60 T or more. When B is less than 6.0 atomic% and C is less than 2.0 atomic%, an amorphous alloy cannot be stably obtained in an Fe-based amorphous alloy. It becomes difficult to make it above. On the other hand, even if B is more than 12.0 atomic% and C is more than 8.0 atomic%, the saturation magnetic flux density is stably 1.60 T or more while the iron loss is stably maintained at 0.100 W / kg or less. It becomes difficult. Therefore, B is limited to a range of 6.0 atomic% to 12.0 atomic%, and C is limited to a range of 2.0 atomic% to 8.0 atomic%.

  Furthermore, in the Fe-based amorphous alloy of this embodiment, when Si or Al is added, the amorphous phase forming ability is improved, and the thermal stability of the amorphous phase is further improved. The contents of Si and Al are 0.10 atomic% or more and 3.0 atomic% or less, 0.10 atomic% or more, and 2.0 atomic% or less, respectively. When Si and Al are less than 0.10 atomic%, the improvement of the amorphous phase forming ability is not observed, and when Si exceeds 3.0 atomic% and Al exceeds 2.0 atomic%, the amorphous phase forming ability is improved. This is because there is not much admission.

  The addition of Mo further improves the ability to form an amorphous phase. The Mo content is set to 0.10 atomic% or more and 6.0 atomic% or less. This is because when Mo is less than 0.10 atomic%, further improvement of the amorphous phase forming ability is not recognized, and when it exceeds 6.0 atomic%, improvement of the amorphous phase forming ability is not recognized so much.

  In an Fe-based amorphous alloy, if 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 a high saturation magnetic flux density of 1.60 T or more. In order to obtain the above, Fe needs to be 80.0 atomic% or more. On the other hand, when the Fe content exceeds 88.0 atomic%, it becomes difficult to form an amorphous phase, and good soft magnetic characteristics (for example, iron loss W13 / 50, which is unique to an amorphous alloy, is stably reduced to 0. .. 100 W / kg or less) is difficult to obtain. Therefore, in the Fe-based amorphous alloy of this embodiment, the Fe content is limited to a range of 80.0 atomic% or more and 88.0 atomic% or less.

  In general, the saturation magnetic flux density is almost determined by the Fe content, and the saturation magnetic flux density increases as the Fe content increases. In the case of the Fe-based amorphous alloy of the present embodiment, elements such as B and C are added to form an amorphous phase. However, the Fe content is lowered correspondingly, and the saturation magnetic flux density obtained is There were restrictions. In the Fe-based amorphous alloy of this embodiment, it is possible to increase the content of Fe by improving the amorphous phase forming ability by newly adding Mo, which is one point. The Fe-based amorphous alloy of the present embodiment could be realized.

In the Fe-based amorphous alloy of the present embodiment, the more preferable range of Fe for obtaining a saturation magnetic flux density of 1.65 T or more can be 84.0 to 88.0 atomic%, and more preferably 84. More than 0.0 atomic% to 88.0 atomic%.
Further, in the Fe-based amorphous alloy of this embodiment, in order to obtain a low iron loss of 0.090 W / kg or less, a more preferable range of Fe can be 80.0 to 84.0 atomic%. .

  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 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 sprays the molten metal on a cooling plate moving at high speed through a slot nozzle or the like, and rapidly quenches and solidifies the molten metal. For example, 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 is equipped with a centrifugal quenching device that uses the inner wall of the drum, a device that uses an endless belt, and an improved auxiliary roll and a roll surface temperature control device, A casting apparatus under reduced pressure or in a vacuum or in an inert gas is also included.

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-described method, an Fe-based amorphous alloy powder excellent in soft magnetic properties can be obtained.

  The Fe-based soft magnetic alloy powder obtained as described above is compacted into a target shape by a mold or the like, and sintered and integrated as necessary, so that the power transformer, high-frequency transformer, and coil are integrated. It can be applied as a use such as an iron core.

  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 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 soft magnetic characteristic was investigated about the obtained thin strip. 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, the plate width was 20 mm because it depends on the length of the slot nozzle, and the length was about 50 m.

  The saturation magnetic flux density of the obtained ribbon was measured using a VSM apparatus (vibrating sample magnetometer). The iron loss of the 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 kHz. 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 a nitrogen atmosphere. 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.

  The measurement results of the saturation magnetic flux density and the iron loss are shown in Table 1 as average values of data at six locations.

  Sample No. in Table 1 As is clear from the results of 1 to 23, Fe is 80.0 atomic% or more and 88.0 atomic% or less, B is 6.0 atomic% or more and 12.0 atomic% or less, and C is 2.0 atomic% or more 8 0.0 atomic% or less, Si from 0.10 atomic% to 3.0 atomic%, Al from 0.10 atomic% to 2.0 atomic%, and Mo from 0.10 atomic% to 6.0 atomic% % Fe or less with a soft magnetic property such that the iron loss at a magnetic flux density of 1.3 T and a frequency of 50 Hz is 0.100 W / kg or less. It was found that an amorphous alloy ribbon was obtained. In addition, in any of the Fe-based amorphous alloy ribbons of the examples, no clear diffraction peak was observed in the X-ray diffraction measurement, and it was confirmed that the ribbon was amorphous.

  In contrast, sample no. Among the comparative examples shown in 24-36, sample No. In Nos. 25, 26, and 28, breakage occurred and waviness occurred on the surface, and saturation magnetic flux density and iron loss could not be measured (indicated by “-” in the column of soft magnetic properties in Table 1).

  Sample No. 25 is an example in which the Fe content exceeded the upper limit of 88.0 atomic% of the desired range. 26 is an example in which the lower limit of the desirable range of B content is below 6.0 atomic%, and sample No. No. 28 is an example in which the C content is below the lower limit of 2.0 atomic% of the desirable range.

  On the other hand, Sample No. In 24, 27, and 29 to 35, even if a ribbon was obtained, the characteristics satisfying both the saturation magnetic flux density of 1.60 T or more and the iron loss of 0.100 W / kg or less were not obtained.

  Sample No. 24 is an example in which the saturation magnetic flux density is lowered when the Fe content falls below the lower limit of 80.0 atomic%, and Sample No. 27 has an upper limit of 12.0 atomic% of the desired range of B content. An example in which the upper iron loss increased, Sample No. 29 is an example in which the upper iron loss increased beyond the upper limit of 8.0 atomic% in which the C content is desirable. Sample No. 30 was an example in which the iron loss increased below the lower limit of 0.10 atomic% in the desired range of the Si content, and sample No. 31 had an iron loss increased above the upper limit of 3.0 atomic% in the Si content. It is an example. Sample No. No. 32 is an example in which the Al content was below the lower limit of 0.10 atomic% and the iron loss increased. 33 is an example where the Al content exceeded the upper limit of 2.0 atomic% and the iron loss increased. Furthermore, sample no. Sample No. 34 is an example in which the iron loss is increased below the lower limit of 0.10 atomic% of the desired range of Mo content, and Sample No. 35 is an example of increase in the iron loss exceeding the upper limit of 6.0 atomic% in the desired range of the Mo content. It is.

  Furthermore, sample no. 36 is an example that does not contain Mo, and since it does not contain Mo, the saturation magnetic flux density of 1.60 T or more and the iron loss of 0.100 W / kg or less were not satisfied.

  From these contrasts, according to the present invention, the Fe-based amorphous alloy has a magnetic flux density of 1.3 T and an iron loss at a frequency of 50 Hz of 0.100 W / kg or less, while maintaining an excellent iron loss. It turns out that improvement can be realized.

(Example 2)
No. in Table 1 About the alloy shown in No. 1, a ribbon was cast by 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, 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 1 to 7, even when a part of 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. It was found that the iron loss can be stably reduced to 0.100 W / kg or less at W13 / 50. Moreover, no clear diffraction peak was observed in any sample in the X-ray diffraction measurement, and it was confirmed that the sample was amorphous.

(Example 3)
No. in Table 1 As for the alloy shown in No. 11, a ribbon was cast 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, 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 clear from the results of 1 to 7, even when a part of 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. It was found that the iron loss can be stably reduced to 0.100 W / kg or less at W13 / 50. Moreover, no clear diffraction peak was observed in any sample in the X-ray diffraction measurement, and it was confirmed that the sample was amorphous.

  According to the present invention, it is possible to stably produce an Fe-based amorphous alloy having high saturation magnetic flux density and low iron loss, that is, good quality, for example, an Fe-based amorphous alloy ribbon on an industrial scale. It became. 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 (3)

Atomic%, Fe is 80.0% or more and 88.0% or less, B is 6.0% or more and 12.0% or less, C is 2.0% or more and 8.0% or less, and Si is 0.10% or more. 3.0% or less, the Al containing 2.0% to 0.10%, further, a Mo containing 6.0% or less 0.10% or more, Ri Do the balance unavoidable impurities,
Magnetic flux density 1.3 T, the iron loss at a frequency 50Hz (W13 / 50) is not more than 0.100W / kg, and the saturation magnetic flux density is characterized in der Rukoto than 1.60T, excellent soft magnetic characteristics Fe-based amorphous alloy.   Soft magnetic properties characterized by replacing Fe of the Fe-based amorphous alloy according to claim 1 within a range of 10.0 atomic% or less with at least one of Ni, Cr, and Co. Excellent Fe-based amorphous alloy. An Fe-based amorphous alloy ribbon comprising the Fe-based amorphous alloy according to claim 1 .