阅读说明：本技术 超软磁性Fe基非晶合金 (Super-soft magnetic Fe-based amorphous alloy ) 是由 井上明久 艾泽那·扎那伊娃 安德烈·巴兹洛夫 亚历山大·丘留莫夫 孔凡利 于 2020-09-11 设计创作，主要内容包括：本发明提供一种具有低矫顽力、高饱和磁通密度、并且有效磁导率极其优异的超软磁性Fe基非晶合金。本发明提供下式(I)的组成式表示的超软磁性Fe基非晶合金：(Fe-(1-X)Ni-(X))-(a)B-(b)P-(c)Si-(d)C-(e) (I)在式(I)中,0.45≤X≤0.65,a、b、c、d和e分别表示原子％,78≤a≤82,10≤b≤13,3≤c≤5,2≤d≤4,0.5≤e≤1,a+b+c+d+e＝100。(The invention provides a super-soft magnetic Fe-based amorphous alloy which has low coercive force, high saturation magnetic flux density and extremely excellent effective magnetic permeability. The present invention provides a super-soft magnetic Fe-based amorphous alloy represented by the compositional formula of the following formula (I): (Fe) 1‑X Ni X ) a B b P c Si d C e (I) In the formula (I), X is more than or equal to 0.45 and less than or equal to 0.65, a, b, c, d and e respectively represent atomic percent, a is more than or equal to 78 and less than or equal to 82, b is more than or equal to 10 and less than or equal to 13, c is more than or equal to 3 and less than or equal to 5, d is more than or equal to 2 and less than or equal to 4, e is more than or equal to 0.5 and less than or equal to 1, and a + b + c + d + e is 100.)

1. An ultra-soft magnetic Fe-based amorphous alloy represented by the compositional formula of the following formula (I):

(Fe_1-XNi_X)_aB_bP_cSi_dC_e (I)

in the formula (I), X is more than or equal to 0.45 and less than or equal to 0.65, a, b, c, d and e respectively represent atomic percent, a is more than or equal to 78 and less than or equal to 82, b is more than or equal to 10 and less than or equal to 13, c is more than or equal to 3 and less than or equal to 5, d is more than or equal to 2 and less than or equal to 4, e is more than or equal to 0.5 and less than or equal to 1, and a + b + c + d + e is 100.

2. The ultra-soft magnetic Fe-based amorphous alloy according to claim 1,

in the formula (I), B/Si is 3-6 (atomic percent).

3. The ultra-soft magnetic Fe-based amorphous alloy according to claim 1 or 2,

in the formula (I), (B + P + C)/Si is 4-8 (atomic percent).

4. The ultra-soft magnetic Fe-based amorphous alloy according to any one of claims 1 to 3,

in formula (I), (B + C)/(P + Si) > 1.4 (atomic percent).

5. The ultra-soft magnetic Fe-based amorphous alloy according to any one of claims 1 to 4,

the effective magnetic permeability (μ e (1kHz)) is 50000 or more.

6. The ultra-soft magnetic Fe-based amorphous alloy according to any one of claims 1 to 5,

in the heat treatment, the glass transition temperature (Tg) of the ultra-soft magnetic Fe-based amorphous alloy is in a region of a low temperature compared to the crystallization start temperature (Tx).

Technical Field

The invention relates to a super-soft magnetic Fe-based amorphous alloy. And more particularly, to an ultra-soft magnetic Fe-based amorphous alloy having a low coercive force, a high saturation magnetic flux density, and an extremely excellent effective magnetic permeability. The super-soft magnetic Fe-based amorphous alloy of the present invention can be suitably applied to low-loss sensors (for example, ultra-high frequency inductors for smart phones having a frequency of 100kHz or higher), magnetic sensors, magnetic shields, magnetic antennas, and the like.

Background

Conventionally, amorphous alloys (amorphous alloys) having an amorphous structure in which atoms are randomly arranged have been found in various alloy groups, and various products utilizing high strength, good soft magnetic characteristics, chemical stability, and the like, which are produced by the atomic arrangement thereof, have been developed. These amorphous alloys can be generally produced by the following method: a method of rapidly cooling an alloy melt to produce a thin strip or the like (liquid quenching method), a method of vapor-depositing the alloy melt in a gas phase, and the like. It is also known that, for an alloy having a specific composition among amorphous alloys, if heating is performed, it is transformed into a supercooled liquid state before reaching a crystallization-starting temperature, resulting in a sharp decrease in viscosity. It is known that such an amorphous alloy having a composition in a supercooled liquid state in a wide range in a low temperature region compared with a crystallization starting temperature constitutes a so-called metal glass alloy (metal glass alloy). The metallic glass alloy exhibits excellent soft magnetic characteristics, and can be formed into a thick sheet material having a large volume, which is much thicker than a thin ribbon of an amorphous soft magnetic alloy obtained by a liquid quenching method, and is used for a wide range of applications. In recent years, research and development have been actively conducted to achieve further performance improvement of such a metallic glass alloy (patent documents 1 to 5).

Patent document 1: japanese laid-open patent publication No. 9-320827

Patent document 2: japanese patent laid-open No. 2001-254159

Patent document 3: japanese laid-open patent publication No. 2002-105607

Patent document 4: japanese patent laid-open publication No. 2009-120927

Patent document 5: japanese patent laid-open No. 2014-31534

Disclosure of Invention

The present invention has been made in view of the above-mentioned conventional circumstances, and an object thereof is to provide a super-soft magnetic Fe-based amorphous alloy having a low coercive force, a high saturation magnetic flux density, and an extremely excellent effective magnetic permeability.

In order to solve the above problems, the present invention provides a super-soft magnetic Fe-based amorphous alloy represented by the compositional formula of the following formula (I).

(Fe_1-XNi_X)_aB_bP_cSi_dC_e (I)

In the formula (I), X is more than or equal to 0.45 and less than or equal to 0.65, a, b, c, d and e respectively represent atomic percent, a is more than or equal to 78 and less than or equal to 82, b is more than or equal to 10 and less than or equal to 13, c is more than or equal to 3 and less than or equal to 5, d is more than or equal to 2 and less than or equal to 4, e is more than or equal to 0.5 and less than or equal to 1, and a + b + c + d + e is 100.

The invention also provides the ultra-soft magnetic Fe-based amorphous alloy in the formula (I), wherein B/Si is 3-6 (atomic percent).

The invention also provides the ultra-soft magnetic Fe-based amorphous alloy in the formula (I), wherein (B + P + C)/Si is 4-8 (atomic percent).

The present invention also provides the above ultra-soft magnetic Fe-based amorphous alloy of (B + C)/(P + Si) > 1.4 (atomic%) in the above formula (I).

The present invention also provides the above-described ultra-soft magnetic Fe-based amorphous alloy having an effective permeability (μ e (1kHz)) of 50000 or more.

Further, the present invention provides the above ultra-soft magnetic Fe-based amorphous alloy having a glass transition temperature (Tg) in a low temperature region compared to a crystallization start temperature (Tx) in heat treatment.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there is provided an ultra-soft magnetic Fe-based amorphous alloy having a low coercive force, a high saturation magnetic flux density, and an extremely excellent effective magnetic permeability.

Detailed Description

The present invention will be described in detail below.

The invention relates to a super-soft magnetic Fe-based amorphous alloy which is represented by a composition formula of a formula (I).

(Fe_1-XNi_X)_aB_bP_cSi_dC_e (I)

In the formula (I), X is more than or equal to 0.45 and less than or equal to 0.65.

In the above formula (I), a, b, c, d and e each represent an atomic%, 78. ltoreq. a.ltoreq.82, 10. ltoreq. b.ltoreq.13, 3. ltoreq. c.ltoreq.5, 2. ltoreq. d.ltoreq.4, 0.5. ltoreq. e.ltoreq.1, and a + b + c + d + e 100.

In the present invention, by setting the values of a, b, c, d, e, and X in the formula (I) to the ranges described above, it is possible to achieve the effects of low coercivity, high saturation magnetic flux density, and very excellent effective magnetic permeability. In the case where any one value deviates from the above range, the effects of the invention of the present application described above cannot be achieved. In the present invention, the high saturation magnetic flux density also includes a moderately high saturation magnetic flux density of 0.6T or more.

In particular, the invention has the following features: an Fe-based amorphous alloy containing Fe and Ni has a composite metalloid composition in which B and Si are combined as metalloids in a specific composition ratio, and these metalloids are added in a predetermined range. Specifically, in the above formula (I), B/Si is set to 3 to 6 (atomic%), and more preferably 4 to 5 (atomic%). By mixing B/Si in the above-described ratio, an amorphous (amorphous) phase exhibiting a glass transition can be obtained in an alloy having a high Ni concentration and a high (Fe + Ni) concentration.

In the formula (I), from the viewpoint of the ability to form an amorphous alloy exhibiting glass transition, (B + P + C)/Si is preferably 4 to 8 (atomic percent), and more preferably 6 to 8 (atomic percent).

In the formula (I), from the viewpoint of the ability to form an amorphous alloy exhibiting glass transition, (B + C)/(P + Si) > 1.4 (atomic percent) is preferable, and 1.6 to 1.9 (atomic percent) is more preferable.

The Fe-based amorphous alloy of the present invention represented by the composition formula of the above formula (I) is a so-called metallic glass, and the glass transition point (glass transition temperature (Tg)) is in a low temperature region compared to the crystallization start temperature (Tx) in the heat treatment. The temperature region between the crystallization start temperature (Tx) and the glass transition temperature (Tg) is called a supercooled liquid region, and is considered to be related to the stability of the glass structure of the metallic glass. Unlike amorphous alloys that do not have supercooled liquid regions, alloys having the above composition do not require extremely high cooling rates when forming glass structures, and therefore metallic glass bulk materials having thicknesses on the order of a few millimeters can be produced.

The ultra-soft magnetic Fe-based amorphous alloy according to the present invention having the above-described configuration can be produced by a method conventionally used.

An alloy having a composition represented by the above formula (I) is cooled and solidified from a molten state (alloy melt) by a pure copper alloy roll quenching method, thereby producing a thin ribbon-like (ribbon-like) or filament-like amorphous alloy ribbon. Alternatively, an amorphous alloy film is formed by a vapor quenching method such as a sputtering method or a steam method. In the case of the single-roll method, the alloy melt may be rapidly cooled in an inert gas atmosphere or a vacuum atmosphere, or may be cooled in an atmospheric atmosphere. When the roll quenching method is used, the peripheral speed of the roll is preferably about 30 to 40m/s, but is not particularly limited.

Subsequently, the ribbon is annealed. The annealing temperature is preferably (Tg-10) K to (Tg-40) K, more preferably (Tg-20) K to (Tg-30) K.

The annealing time is preferably about 5 to 45 minutes, and more preferably about 10 to 30 minutes. The annealing atmosphere is not particularly limited, and examples thereof include vacuum, argon, and nitrogen atmospheres.

The ultra-soft magnetic Fe-based amorphous alloy of the present invention obtained as described above has an excellent effect of having a saturation magnetic flux density (Bs) of 0.6T or more.

Further, the coercive force (Hc) can be kept at a low value of 1A/m or less.

In addition, an extremely excellent effect of having an effective permeability (1kHz) of 50000(μ e) or more can be obtained.

The amorphous alloys of the present invention are in the form of "metallic glasses". In the present invention, the "metallic glass" refers to an alloy in which only a gentle peak (glass phase) is present and no peak is present in an X-ray diffraction pattern obtained by measuring the alloy by a normal X-ray diffraction method.

When the temperature of the amorphous alloy of the present invention is raised, rapid softening accompanied by the glass transition phenomenon can be observed. This softening phenomenon is a phenomenon peculiar to metallic glass, and can be processed into various shapes within a time range before crystallization starts by heating to a glass transition temperature (Tg) or higher. The glass transition phenomenon can be measured by various methods such as thermomechanical analysis (TMA), and the Fe-based metallic glass of the present invention can be processed by selecting a temperature suitable for the processing method of the member. In the Fe-based metallic glass (metallic glass single phase) of the present invention, the temperature interval of the supercooled liquid region represented by the formula of the temperature difference Δ Tx (Δ Tx ═ Tx-Tg) between the crystallization start temperature (Tx) and the glass transition temperature (Tg) is usually 15K or more, and preferably 20K or more, when measured at a temperature rise rate of 40K/min.

The heat treatment of the sample to be applied for obtaining the amorphous alloy of the present invention is not particularly limited, and the following methods may be mentioned: vacuum packaging in the prior art, and placing the packaged product into a heat treatment furnace for rapid heating and rapid cooling.

However, in the case of a material exhibiting super soft magnetism as in the amorphous alloy of the present invention, the following method is preferable as compared with the above-described conventional heat treatment method: wrapping the sample in aluminum foil (foil) or copper foil, and heat treating in ash powder, carbon powder, fine sand or ferric oxide fine powder heated to specified temperature in advance. By performing the above heat treatment, the heating can be completed quickly by heating to a predetermined temperature at a much faster heating rate. By performing the heat treatment, the heating can be completed quickly by heating to a predetermined temperature at an extremely high heating rate.

As a result, in the ultra-soft magnetic Fe-based amorphous alloy of the present invention, by precise temperature control, heat treatment can be performed for a short time at a temperature close to the crystallization temperature, and more excellent soft magnetism (low coercive force, high magnetic permeability) can be obtained.

[ examples ]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.

(examples 1 to 9, comparative examples 1 to 4)

A thin ribbon of an amorphous phase having a thickness of 0.02mm was prepared by a single-roll liquid quenching method using an alloy having the composition shown in table 1 below. Next, the ribbon is annealed in a nitrogen atmosphere. The annealing temperature and annealing time are shown in table 1. The annealing temperatures in the examples are all 20K below Tg. In addition, Tx1 shown in the annealing temperature column of the comparative example is the first crystallization onset temperature when the heat quantity of differential scanning is measured at a temperature rising rate of 0.67K/s. That is, the annealing in the comparative example was performed at a temperature 20 to 35K lower than Tx 1.

[ alloy Structure ]

From the X-ray diffraction pattern, it was confirmed that the structure of the alloy after annealing exhibited only a broad peak, and Am (amorphous ). In table 1 below, "Am + bcc" is a structure in which a peak is present in addition to a broad peak in the X-ray diffraction pattern, and is a structure in which a state in which bcc phases (crystal phases) of Am and Fe coexist is confirmed.

[ confirmation of glass transition temperature (Tg) ]

The start temperature of the endothermic reaction on a DSC curve obtained by measurement at a temperature increase rate of 20 to 40K/min using a Differential Scanning Calorimeter (DSC) is confirmed.

[ measurement of saturated magnetic flux Density ]

The measurement was performed in a magnetic field of 2T using a Vibrating Sample Magnetometer (VSM).

[ measurement of Hc (coercive force) ]

The magnetic load up to 200A/m was measured using a magnetic field-magnetic (B-H) loop analyzer.

[ μ e (effective permeability) ]

The measurement was carried out in an alternating magnetic field of 5mA/m over a wide range from 0.1kHz to 10MHz using an impedance analyzer. Table 1 shows the measurement results at 1 kHz. In addition, the sample is a strip sample with the length of 7-9 cm or a strip sample with the length of 60 cm.

The results are shown in table 1.

[ Table 1]

As shown in Table 1, it was confirmed that all the samples shown in examples 1 to 9 were constituted only of an amorphous phase (amorphous phase). The saturation magnetic flux density (Bs) is 0.6T or more, and the coercive force (Hc) is 1A/m or less. Further, it was confirmed that the effective permeability (μ e) at 1kHz was 50000 or more, having excellent soft magnetic characteristics.

In comparative examples 1 to 4, no glass transition point (Tg) was observed. In addition, these comparative examples cannot obtain low coercive force, and the effective permeability can only obtain a value far lower than 50000.

In addition, comparative examples 1 and 2 are alloys deviating from the composition ratio range of Fe and Ni in formula (I), and comparative example 4 is an alloy deviating from the ranges of a and b (atomic%). Comparative example 3 is an alloy that deviates from the scope of the present invention except for a and e (atomic%).

Industrial applicability

The super-soft magnetic Fe-based amorphous alloy of the present invention has a low coercive force, a high saturation magnetic flux density, and an extremely excellent effective magnetic permeability, and therefore can be suitably applied to low-loss inductors (for example, ultra-high frequency inductors for smartphones having a frequency of 100kHz or higher), magnetic sensors, magnetic shields, magnetic antennas, and the like as an excellent super-soft magnetic material.