KR102280574B1 - iron base metal glass alloy powder - Google Patents

Abstract

According to the present invention, at least one small amount of supercooling degree improving element selected from the group consisting of iron-based metal elements mainly composed of Fe, the group of semimetal elements consisting of Si, B, P and C, and the group consisting of Nb and Mo It is an iron-based metallic glass alloy powder containing a group and optionally a corrosion-resistance modifying component, the iron-based metallic glass alloy having a particle diameter of 30 µm or less with the total amount of the semimetal element group and the total amount of the corrosion-resistance modifying component within a predetermined range powder is provided.

Description

iron base metal glass alloy powder

The present invention relates to a flame-retardant iron-based metal-glass alloy powder that can be used as a magnetic material for electronic components such as inductors and choke coils.

Metallic glass is one type of amorphous metal, and so far, hundreds of alloy compositions such as iron group and titanium group have been discovered. Among them, since an iron-based metal glass alloy has excellent magnetic properties when compacted, magnetic materials for manufacturing electronic components such as inductors and choke coils, electromagnetic shields, for example, materials such as noise suppression sheets for electronic components It is expected to be used in a wide range of applications, such as (Patent Document 1).

Since the noise suppression sheet is generally used in the vicinity of an electronic device that generates heat, flame retardancy is required, and a noise suppression sheet made flame retardant by including a large proportion of flat soft magnetic material powder has been reported (Patent Document 2) . A noise suppression sheet made flame retardant by including nanocrystal soft magnetic metal powder and acrylic binder resin has also been reported (Patent Document 3). However, the flame retardance evaluated by these patent documents is the flame retardance of a sheet|seat, and is not flame retardance of a powder.

Ignition property is not a problem specific to the final product, but also a problem in the state of the material such as powder before forming the final product. This is because there is a risk that the material may ignite during handling during or after production. Care must also be taken when storing the material until the final product is formed, or when transporting it to a separate location to make the final product.

A powder having excellent flame retardancy, containing predetermined amounts of Al and/or Si, Cr, and O, for flame-retardant magnetic shielding with a _{D 50} of 10 to 40 μm and an aspect ratio (D _{50 /d) of 20 to 200} A flat iron-based alloy powder has been reported (Patent Document 4). Flat iron for flame-retardant magnetic shields containing predetermined amounts of Al and/or Si, Cr, O, and N, and having a D ₅₀ of 10 to 40 μm and an aspect ratio (D _{50 /d) of 20 to 200} Alloy powder has also been reported (Patent Document 5). Although these patent documents evaluate the flame retardance of a powder, the powder is not an amorphous powder.

On the other hand, the inductor is used in a mobile device such as a smart phone or an electric vehicle system such as a power steering or an airbag. In recent years, high-frequency circuits for the purpose of high-speed arithmetic processing of CPUs have been advanced. With the increase in frequency, it has become a form that requires a large current for the inductor. Usually, the size of the inductor increases with increasing current, but the size of the inductor can be reduced by using a material with high saturation magnetization. From such circumstances, saturation magnetization, which is a magnetic property of a magnetic material constituting the inductor, has become important.

As a material with high saturation magnetization, there is a metal material mainly made of Fe. However, since a metal material has high conductivity and is used in a bulk form in a high-frequency circuit, an eddy current loss becomes large, so it cannot be used in a bulk form. In general, the iron loss of the soft magnetic material (general term for energy loss due to the magnetic material in the inductor) can be expressed by the following modified Steinmetz equation.

Core loss of soft magnetic material = hysteresis loss + eddy current loss

Since the eddy current loss depends on the grain size, it is effective to reduce the grain size in order to reduce the iron loss by reducing the eddy current loss.

On the other hand, it is known that an amorphous material exhibits excellent soft magnetic properties of low iron loss since there is no anisotropy derived from the crystal structure.

In order to reduce the size of an inductor to be mounted on a mobile device or an electronic system, it is required to have an iron-based metal glass alloy powder containing Fe as a main component and a small particle diameter.

Japanese Patent Laid-Open No. 2014-169482 Japanese Patent Laid-Open No. 2009-59753 Japanese Patent Laid-Open No. 2004-288941 Japanese Patent Laid-Open No. 10-4004 Japanese Patent Laid-Open No. 10-121103

Until now, several iron-based metal glass alloy powders having an amorphous composition have been found, and reported by the applicant of the present application, Japanese Patent Application Laid-Open No. 2005-290468 and Japanese Patent Application Laid-Open No. 2014-169482, etc. However, it is not known that the iron-based metal glass alloy powder is easily ignited.

Accordingly, an object of the present invention is to solve the problem of ignitability of the iron-based metal-glass alloy powder, and an object of the present invention is to provide a flame-retardant iron-based metal-glass alloy powder.

As a result of earnest examination by this inventor, it succeeded in setting it as a flame retardance by adjusting the composition of iron-base metal glass alloy powder. That is, according to the present invention, the following iron-based metal glass alloy powder is provided:

[1] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤22, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6:1),

(2.5:7.5)≤(a:b)≤(5.5:4.5) and

(5.5:4.5)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the iron-based metal glass alloy further contains at least one selected from the group consisting of Cr and Zr as a corrosion resistance modifying component, , the content rate of the corrosion resistance modifying component is 2.8 to 5.5 wt% based on the total mass of the alloy component,

The particle diameter is 0.5 μm or more, less than 3 μm,

The iron-based metal glass alloy powder.

[2] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _{1 -s- t} Co _s Ni _t ) _{100-x- y} {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤26, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6:1),

(2.5:7.5)≤(a:b)≤(5.5:4.5) and

(5.5:4.5)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the iron-based metal glass alloy further contains at least one selected from the group consisting of Cr and Zr as a corrosion resistance modifying component, , the content rate of the corrosion resistance modifying component is 2.3 to 5.5 wt% based on the total mass of the alloy component,

Particle diameter is 3 μm or more, less than 10 μm,

The iron-based metal glass alloy powder.

[3] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤26, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6:1),

(2.5:7.5)≤(a:b)≤(5.5:4.5) and

(5.5:4.5)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the particle diameter is 10 to 30 μm,

The iron-based metal glass alloy powder.

[4] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤22, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6.1:1),

(2.5:7.5)≤(a:b)≤(5.6:4.4) and

(4.2:5.8)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the iron-based metal glass alloy further contains at least one selected from the group consisting of Cr and Zr as a corrosion resistance modifying component, , the content rate of the corrosion resistance modifying component is 2.8 to 5.5 wt% based on the total mass of the alloy component,

The particle diameter is 0.5 μm or more, less than 3 μm,

The iron-based metal glass alloy powder.

[5] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤26, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6.1:1),

(2.5:7.5)≤(a:b)≤(5.6:4.4) and

(4.2:5.8)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the iron-based metal glass alloy further contains at least one selected from the group consisting of Cr and Zr as a corrosion resistance modifying component, , the content rate of the corrosion resistance modifying component is 2.3 to 5.5 wt% based on the total mass of the alloy component,

Particle diameter is 3 μm or more, less than 10 μm,

The iron-based metal glass alloy powder.

[6] an iron-based metal glass alloy powder,

The iron-based metal glass alloy has the following composition formula:

(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y

is expressed as

The composition ratio of the ferrous metal element group Fe, Co and Ni is 19≤x≤26, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,

The composition ratio of the semimetal element groups Si, B, P and C is,

(0.5:1)≤(m:n)≤(6.1:1),

(2.5:7.5)≤(a:b)≤(5.6:4.4) and

(4.2:5.8)≤(c:d)≤(9.5:0.5),

The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the particle diameter is 10 to 30 μm,

The iron-based metal glass alloy powder.

[7] The iron-based metallic glass alloy contains, as a corrosion resistance modifying component, at least one selected from the group consisting of Cr and Zr, based on the total mass of the alloy component, exceeding 0 wt% and not more than 5.5 wt% The iron-based metal glass alloy powder according to [3] or [6], further contained in a proportion.

[8] The iron-based metal glass alloy powder according to [1], [2], [4], [5] or [7], wherein the corrosion resistance modifying component is Cr.

[9] A molded article produced using the iron-based metal glass alloy powder according to any one of [1] to [8].

According to the present invention, it is possible to provide a flame-retardant iron-based metal glass alloy powder. By eliminating the risk of ignition of the material during handling during or after production, the storage and transportation method until the final product is formed can be simplified, so that safe and low-cost material can be used.

In addition, the iron-based metal glass alloy powder of the present invention maintains high magnetic properties. For this reason, it can be suitably used as a material for powder molding of various electronic parts, or a material for a coating material for forming a magnetic film on an electronic circuit board or the like.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the concept of the water atomizing apparatus used for manufacture of the iron-based metal glass alloy powder of this invention.

In the present specification, the elements constituting the "iron group metal element group" are Fe, Co, and Ni.

In the present specification, the elements constituting the "group of semimetal elements" are Si, B, P, and C.

In the present specification, the elements constituting the “group of elements for improving the degree of supercooling” are Nb and Mo.

In the present specification, the "content" of the component elements of the alloy refers to the content of the component elements based on the total mass of the iron-based glass alloy powder containing the additional elements (corrosion resistance modifying component, corrosion resistance modifying subcomponent) with respect to the composition formula (wt) %) is shown. In addition, the composition ratio in the said compositional formula shows atomic% (at%) or an atomic ratio unless otherwise stated.

In this specification, the term "particle diameter" refers to an average particle diameter (median diameter, D ₅₀ ) unless otherwise specified.

In the composition formula (basic composition), by adjusting each composition ratio, a flame retardant iron-based metallic glass alloy can be obtained even if the particle diameter is smaller than that of a conventional product. The present invention includes the first to third aspects classified by composition ratio and particle size. In addition, in this specification, unless otherwise indicated, "this invention" refers to the whole form.

The first aspect is an iron-based metallic glass mainly characterized in that 19≤x≤22, the corrosion resistance modifying component is 2.8 to 5.5 wt% based on the total mass of the alloy component, and the particle size is 0.5 µm or more and less than 3 µm It relates to alloy powder.

The second aspect is an iron-based metallic glass mainly characterized in that 19≤x≤26, the corrosion resistance modifying component is 2.3 to 5.5 wt% based on the total mass of the alloy component, and the particle size is 3 µm or more and less than 10 µm It relates to alloy powder.

The third aspect is an iron-based metal glass alloy powder mainly characterized in that 19≤x≤26, the corrosion resistance modifying component is 0 to 5.5 wt% based on the total mass of the alloy component, and the particle diameter is 10 to 30 μm. is about

First, the matter common to the whole form is demonstrated below, then the individual matter to each form.

1. Composition ratio with respect to the whole form

1-1. Composition ratio of ferrous metal element group (s, t, s+t)

In the above basic composition, the composition ratio of the iron-based metal element group is 0≤s≤0.35, 0≤t≤0.35, and s+t≤0.35.

s and t may be zero. That is, it is not necessary to contain Co or Ni, which are iron-based metal elements other than Fe. Although Co and Ni are expensive, even if they are not included, since they have excellent magnetic properties and corrosion resistance, and a degree of supercooling of 40K or more can be obtained, an iron-based metal glass alloy powder can be obtained at a lower cost.

At s+t>0.35, the content of Co or Ni increases and the material cost increases, and the degree of subcooling becomes so small that the degree of subcooling cannot be measured. As a result, a degree of supercooling of 40K or higher, which is a condition for forming an amorphous composition, cannot be obtained.

1-2. Composition ratio of semimetal element group (a, b, m, c, d, n)

The range of the composition ratio (a, b, m, c, d, n) of each element constituting the group of semimetal elements is within the range of the composition ratio (x) of the sum,

(0.5:1)≤(m:n)≤(6.1:1),

(2.5:7.5)≤(a:b)≤(5.6:4.4) and

(4.2:5.8)≤(c:d)≤(9.5:0.5)

do it with Preferably,

(0.5:1)≤(m:n)≤(6:1),

(2.5:7.5)≤(a:b)≤(5.5:4.5) and

(5.5:4.5)≤(c:d)≤(9.5:0.5)

do it with

When the composition ratio of the semimetal element group is out of the above range, it is difficult to obtain a degree of supercooling of ΔTx≥40K.

The composition ratio of the group of semimetal elements is

(1.5:1)≤(m:n)≤(5.5:1),

(3.5:6.5)≤(a:b)≤(6.5:3.5) and

It is preferable to set it as (6.0:4.0)<=(c:d)<=(8.5:1.5).

More preferably,

(2.5:1)≤(m:n)≤(3.5:1),

(4.3:5.7)≤(a:b)≤(5.2:4.8) and

(6.5:3.5)≤(c:d)≤(7.0:3.0).

By setting the ratio of the metalloid element group to such a range, the magnetic properties and corrosion resistance of the iron-based metal glass alloy powder can be further improved.

1-3. Composition ratio of subcooling improvement element group (y)

The composition ratio of the supercooling degree improving element group is 0≤y≤6.0, preferably 0.05≤y≤2.4, more preferably 0.15≤y≤1.3. By setting the composition ratio of the supercooling degree improving element group to such a range, magnetic properties can be improved. However, since Nb or Mo is an expensive rare metal, it is preferable that the composition ratio of Nb or Mo is as low as possible within the range where the required magnetic properties are obtained. When the composition ratio of the supercooling degree improving element group is excessive, the supercooling degree improvement effect reaches a saturation value and the magnetic properties tend to be relatively deteriorated.

In addition, the reason that the composition ratio of either one of Nb or Mo and the composition ratio of the sum total is made same is because both elements have similar chemical properties, and an atomic radius and atomic weight approximate.

2. Composition ratio and particle size for each form

2-1. first form

2-1-1. Composition ratio of semimetal element group (x)

The composition ratio (x) of the sum total of the metalloid element group in a 1st aspect is 19<=x<=22.

From the viewpoints of flame retardancy, degree of subcooling and magnetic properties, the range of 21≤x≤22 is preferable.

In addition, the lower limit of x was set from a viewpoint of obtaining the degree of supercooling of ΔTx≥40K and obtaining an amorphous single phase. The upper limit of x was set in consideration of, first, from the viewpoint of flame retardancy, and secondly, suppression of magnetic properties deterioration accompanying a decrease in Fe amount and suppression of material cost.

2-1-2. corrosion-resistance modifier

The content rate of the corrosion resistance modifying component in the first aspect is 2.8 to 5.5 wt%, preferably 2.8 to 4.0 wt%, based on the total mass of the alloy component. Since an oxide film is formed on the surface of the iron-based metallic glass alloy powder by Cr and Zr contained in the iron-based metallic glass alloy powder, corrosion resistance is improved. As a corrosion-resistance modifying component, Cr is preferable from an economical reason.

The iron-based metal glass alloy powder of the first aspect of the present invention may further contain Al as a corrosion resistance modifying component. Although Al also forms an oxide film on the surface of the iron-based metal glass alloy powder, there is an effect of increasing the hardness of the oxide film formed by Cr and/or Zr. When the hardness of the oxide film is increased, the corrosion resistance is further improved. In addition, when manufacturing iron-based metal glass alloy powder by the atomization method mentioned later, Al contributes to spheroidization of a powder.

When containing Al, the content rate of Al is 0.01 to 0.75 wt% based on the total mass of the iron-based metal glass alloy powder of the first aspect of the present invention, and the content rate of the corrosion resistance modifying component containing Al is 1.0 to It is preferable that it is 5.0 wt%. Furthermore, it is preferable that the content rate of Al is 0.03 to 0.50 wt%, and the content rate of the corrosion resistance modifying component containing Al is 1.5 to 1.9 wt%. In the case of the latter composition, not only corrosion resistance but also magnetic properties are further improved.

The iron-based metal glass alloy powder of the first aspect of the present invention may further contain at least one selected from the group consisting of V, Ti, Ta, Cu and Mn as the corrosion-resistance modifying subcomponent. Thereby, excellent magnetic properties are obtained while reducing the content of the corrosion resistance modifying component. The total content of the corrosion-resistance-modifying subcomponent is 0.03 to 0.70 wt%, further 0.05 to 0.50 wt%, and 0.10 to 0.30 wt%, based on the total mass of the iron-based metal glass alloy powder of the first aspect of the present invention. desirable. Like Al, the corrosion-resistance-modifying subcomponent can also improve corrosion resistance by forming an oxide film on the surface of the iron-based metal glass alloy powder. In addition, the specific resistance of the iron-based metal glass alloy powder can be improved by a synergistic effect with the corrosion resistance modifying component.

2-1-3. particle diameter

The particle diameter of the iron-based metallic glass alloy powder of the first aspect of the present invention is 0.5 µm or more and less than 3 µm. In general, the smaller the particle size, the lower the eddy current loss in iron loss, which is advantageous in that it has excellent magnetic properties, but it is disadvantageous in that the specific surface area increases, so that the reactivity increases and the reliability of the material decreases. However, if it is the iron-based metal glass alloy powder of the composition of the 1st aspect of this invention, such a fault can be eliminated. Also, in general, when the particle diameter is small, the iron-based metal glass alloy powder is easily corroded, but the iron-based metal glass alloy powder of the first aspect of the present invention is 0.5 µm or more, and corrosion resistance even with a small particle diameter such as less than 3 µm good

2-2. second form

2-2-1. Composition ratio of semimetal element group (x)

The composition ratio (x) of the sum total of the metalloid element group in a 2nd aspect is 19<=x<=26. From the viewpoints of flame retardancy, degree of supercooling and magnetic properties, the range of 21≤x≤26 is preferable.

In addition, the lower limit of x was set from a viewpoint of obtaining the degree of supercooling of ΔTx≥40K and obtaining an amorphous single phase. The upper limit of x was set in consideration of, first, from the viewpoint of flame retardancy, and secondly, suppression of magnetic properties deterioration accompanying a decrease in Fe amount and suppression of material cost.

2-2-2. corrosion-resistance modifier

The content rate of the corrosion resistance modifying component in the second aspect is 2.3 to 5.5 wt%, preferably 2.3 to 4.0 wt%, based on the total mass of the alloy component. Since an oxide film is formed on the surface of the iron-based metallic glass alloy powder by Cr and Zr contained in the iron-based metallic glass alloy powder, corrosion resistance is improved. As a corrosion-resistance modifying component, Cr is preferable from an economical reason.

For the further explanation of the corrosion resistance modifying component (Al) and the corrosion resistance modifying subcomponent (at least one selected from the group consisting of V, Ti, Ta, Cu and Mn), the description of the first aspect is incorporated.

2-2-3. particle diameter

The particle diameter of the iron-based metallic glass alloy powder of the second aspect of the present invention is 3 µm or more and less than 10 µm. In general, the smaller the particle size, the lower the eddy current loss in iron loss, which is advantageous in that it has excellent magnetic properties, but it is disadvantageous in that the specific surface area increases, so that the reactivity increases and the reliability of the material decreases. However, if it is the iron-based metal glass alloy powder of the composition of the 2nd aspect of this invention, such a fault can be eliminated. Also, in general, when the particle diameter is small, the iron-based metal glass alloy powder is easily corroded, but the iron-based metal glass alloy powder of the second aspect of the present invention is 3 µm or more, and corrosion resistance even with a small particle diameter such as less than 10 µm good

2-3. 3rd form

2-3-1. Composition ratio of semimetal element group (x)

The composition ratio (x) of the sum total of the metalloid element group in a 3rd aspect is 19<=x<=26. From the viewpoints of flame retardancy, degree of supercooling and magnetic properties, the range of 21≤x≤26 is preferable.

In addition, the lower limit of x was set from a viewpoint of obtaining a supercooling degree of ΔTx≥40K and obtaining an amorphous single phase. The upper limit of x was set in consideration of, first, from the viewpoint of flame retardancy, and secondly, suppression of magnetic properties deterioration accompanying a decrease in Fe amount and suppression of material cost.

2-3-2. corrosion-resistance modifier

The content rate of the corrosion resistance modifying component in the third aspect is 0 to 5.5 wt%, preferably 3.0 to 4.0 wt%, based on the total mass of the alloy component. Since an oxide film is formed on the surface of the iron-based metallic glass alloy powder by Cr and Zr contained in the iron-based metallic glass alloy powder, corrosion resistance is improved. As a corrosion-resistance modifying component, Cr is preferable from an economical reason.

For the further explanation of the corrosion resistance modifying component (Al) and the corrosion resistance modifying subcomponent (at least one selected from the group consisting of V, Ti, Ta, Cu and Mn), the description of the first aspect is incorporated.

2-3-3. particle diameter

The particle diameter of the iron-based metal glass alloy powder of the 3rd aspect of this invention is 10-30 micrometers. In general, the smaller the particle size, the lower the eddy current loss in iron loss, which is advantageous in that it has excellent magnetic properties, but it is disadvantageous in that the specific surface area increases, so that the reactivity increases and the reliability of the material decreases. However, if it is the iron-based metal glass alloy powder of the composition of the 3rd aspect of this invention, such a fault can be eliminated. In general, if the particle diameter is small, the iron-based metal glass alloy powder is easily corroded, but the iron-based metal glass alloy powder of the third aspect of the present invention has good corrosion resistance even with a small particle diameter such as 10 to 30 µm.

3. Manufacturing method

The iron-based metal glass alloy powder of the present invention can be produced by the water atomization method. The water atomization method is a method in which iron-based metal glass alloy powder can be manufactured in the air, and can be manufactured at low equipment and manufacturing costs.

The atomizing apparatus of the water atomization method is a melting crucible 1 in which a bottom plate in which a molten metal orifice 5 is drilled downwardly is integrally formed on a side plate erected in a cylindrical shape as shown in FIG. 1, and the An induction heating coil (2) spirally arranged on the entire outer peripheral surface of the side plate of the melting crucible (1), and a molten metal stopper (3) charged in the melting crucible (1) for opening and closing the melting crucible (1); An atomizing nozzle 6 disposed below the molten metal orifice 5 is provided.

In the melting crucible 1, a molten raw material 4 corresponding to the iron-based metallic glass alloy powder of the present invention (basic composition, corrosion-resistance modifying component, and, if necessary, corrosion-resistance modifying subcomponent), iron-based metallic glass alloy powder is prescribed Adjust the ratio so that the composition of Next, the molten raw material 4 is heated by the induction heating coil 2 to a melting point or higher to obtain a molten metal. Next, the molten metal orifice 5 is opened with the molten metal stopper 3 , and the molten metal (molten raw material 4 ) is dropped from the molten metal orifice 5 . The atomizing nozzle 6 sprays water so as to form a water film below the molten metal orifice 5 . The molten metal that has fallen from the molten metal orifice 5 collides with the water film, is crushed, and is rapidly cooled and solidified. The molten metal solidified into powder falls into the water 8 in a water tank (not shown) disposed below the atomizing nozzle, and further cooled. This powder is collect|recovered, and the iron-based metal glass alloy powder of the target composition and particle size is obtained through a drying process and a classification process.

The iron-based metallic glass alloy powder of the present invention does not crystallize even when the iron-based metallic glass alloy powder is prepared at a slower cooling rate compared to the conventional iron-based metallic glass alloy. That is, even in a general-purpose mass production facility with a slow cooling rate, it becomes possible to easily produce an amorphous single-phase iron-based metal glass alloy powder containing no crystalline phase. This is because the degree of undercooling ΔTx expressed by the difference between the crystal initiation temperature Tx and the glass transition temperature Tg is large, and the amorphous forming ability is improved.

Since the iron-based metal-glass alloy powder obtained through the above process has a high sphericity, for example, the iron-based metal-glass alloy powder is filled with a molding die to obtain a magnetic core, etc. When formed, since the packing density of the iron-based metal glass alloy powder can be increased, products such as electronic components having excellent magnetic properties can be manufactured.

In the present invention, the particle diameter of the iron-based metal glass alloy powder can be controlled by changing the production conditions of the water atomization method, or powder having a desired particle diameter can be obtained by classifying using a sieve or the like.

Example

The basic composition and the corrosion resistance modifying component were adjusted so that the content ratio of the corrosion resistance modifying component was shown in the table below, the obtained material mixture was melted in a high frequency induction furnace, and a powder having the desired composition was obtained by water atomization under the following conditions. .

<Water atomization conditions>

· Water pressure: 100 MPa

Quantity: 100L/min

· Water temperature: 20℃

· Orifice diameter: φ4mm

· Molten metal raw material temperature: 1,500℃

_{The obtained iron-based metal glass alloy powder was classified at D 50} =2±0.3 µm using an air flow classifier (manufactured by Nisshin Engineering & Construction: Turbo Crusher). The particle diameter was measured with a laser diffraction type particle size distribution analyzer (Microtrac MT3300EX II (wet type) manufactured by Nikkiso Corporation). The content rate of the metalloid element and the supercooling degree improving element was measured with an ICP emission analyzer (manufactured by Hitachi High-Tech Sciences: SPS3500DD).

<Evaluation of flame retardancy>

The ignitability of the obtained iron-based metallic glass alloy powders of 1st - 3rd forms was investigated by the small gas flame ignition test of the Dangerous Substances Class 2 test method prescribed by the Fire Protection Law. Specifically, the evaluation powder is expanded into a hemispherical shape having a width of 30 mm and a height of 15 mm. Using a simple ignition mechanism (portable simple gas lighter) with a flame length of 70 mm, the sample is brought into contact with a flame at a contact angle of 30 degrees for 10 seconds. If combustion does not continue, this operation is repeated 10 times. Among samples that have been ignited at least once and continue to burn flame or smokeless combustion even after the flame is extinguished, if ignition is within 3 seconds, easy ignition (Class 1 flammable solid), if ignited within 10 seconds after exceeding 3 seconds Although it is judged that it is ignitable (type 2 flammable solid), in this evaluation, if it ignites within 10 seconds, since it becomes a dangerous substance, it was judged that it is ignitable. When it ignited for more than 10 second or combustion was not continued, it was judged that there is no ignition property. The presence or absence of ignition was evaluated based on the following evaluation classification. The results are put together in the table below.

<Evaluation Category>

○: non-ignition

×: ignition

Table 4 shows the composition of the iron-based metal glass alloy powder of the second embodiment, and the particle size is 3 µm or more and less than 10 µm. For these powders, since it can be expected from the results of Tables 1 to 3 that non-combustion is achieved even if the powder has a small particle size and is non-igniting, a flame retardancy test was not performed.

In addition, the symbol "*" attached to the upper right of the number in the "example" column indicates that it is a comparative example. In addition, the symbol "*" attached to the upper right of the number in the y column indicates that M is Mo.

The iron-based metal glass alloy powder of the present invention can be suitably used as a magnetic material for manufacturing electronic components such as inductors and choke coils, as well as materials for electromagnetic shielding, noise suppression sheets, noise suppression filters, and the like. The iron-based metal glass alloy powder of the present invention can also be used for a projection material or an abrasive material.

1: melting crucible
2: Induction heating coil
3: Molten metal stopper
4: molten raw material
5: Orifice
6: atomize nozzle
7: water curtain
8 : water

Claims (9)

It is an iron-based metal glass alloy powder,
The iron-based metal glass alloy has the following composition formula:
(Fe _1-st Co _s Ni _t ) _100-xy {(Si _a B _b ) _m (P _c C _d ) _n } _x M _y
is expressed as
The composition ratio of the ferrous metal element group Fe, Co and Ni is 21≤x≤22, 0≤y≤6.0, 0≤s≤0.35, 0≤t≤0.35 and s+t≤0.35,
The composition ratio of the semimetal element groups Si, B, P and C is,
(2.5:1)≤(m:n)≤(3.5:1),
(4.3:5.7)≤(a:b)≤(5.2:4.8) and
(6.5:3.5)≤(c:d)≤(7.0:3.0),
The supercooling degree improving element group M is at least one selected from the group consisting of Nb and Mo, and the iron-based metal glass alloy further contains at least one selected from the group consisting of Cr and Zr as a corrosion resistance modifying component, , the content rate of the corrosion resistance modifying component is 2.8 to 5.5 wt% based on the total mass of the alloy component,
The particle diameter is 0.5 μm or more, less than 3 μm,
The iron-based metal glass alloy powder. The iron-based metal glass alloy powder according to claim 1, wherein the corrosion resistance modifying component is Cr. A molded article produced using the iron-based metal glass alloy powder according to claim 1. delete delete delete delete delete delete

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