JPH0851010A - Green compact of soft magnetic alloy, production method thereof and coating powder therefor - Google Patents

Abstract

PURPOSE:To ensure high saturation magnetic flux density and high magnetic permeability by providing alloy particles of Fe or Co containing one or more than one kind of element selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, Si, B or Al, and an inorganic insulator present in the grain boundary. CONSTITUTION:An amorphous alloy powder, having a composition containing at least one of Fe or Co and added with one or more than one kind of element M selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, Si, B or Al or a composition of Fe-B added with one or more than one kind of element selected from Ti, Zr, Hf, V, Nb, Ta, Mo or W, is coated with a compositional element of an inorganic insulator. It is then heat treated under pressure to produce a coated powder 3 where the powder 2 is coated uniformly with a coating 1 having thickness of submicron order. Thickness of the coating 1 can be regulated depending on the concentration of alkoxide dissolved into a solution.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a soft magnetic alloy compact, which is used for a core of a magnetic head, a magnetic core of a pulse motor, etc., a method for producing the compact, and a coating powder for forming a soft magnetic alloy compact.

[0002]

2. Description of the Related Art Generally, soft magnetic alloys used in cores of magnetic heads, magnetic cores of pulse motors, transformers, choke coils, etc. are required to have high saturation magnetic flux density and high magnetic permeability. It has a low coercive force and is easy to obtain a thin shape. Therefore, in the development of soft magnetic alloys, material research has been conducted in various alloy systems from these viewpoints. Conventionally, crystalline alloys such as sendust, permalloy, and silicon steel have been used as materials for the above-mentioned applications. In particular, recently, Fe-based and C-based alloys have been used.
O-based amorphous alloys are also being used.
However, in the case of a magnetic head, a higher performance magnetic material for a magnetic head is desired in order to cope with the increase in coercive force of a magnetic recording medium accompanying the increase in recording density. In the case of pulse motors, transformers, choke coils, etc., downsizing,
A material having more excellent magnetic properties is desired in order to cope with higher frequencies.

[0003]

However, although the sendust is excellent in soft magnetic characteristics, it has a drawback that the saturation magnetic flux density is as low as about 11 kG. Permalloy similarly has an alloy composition excellent in soft magnetic characteristics. Has a low saturation magnetic flux density of about 8 kG, and silicon steel has a high saturation magnetic flux density but a poor soft magnetic property. on the other hand,
Co-based amorphous alloys have excellent soft magnetic properties,
The saturation magnetic flux density is insufficient at about 10 kG. Also, F
The e-based amorphous alloy has a high saturation magnetic flux density and can have a saturation magnetic flux density of 15 kG or more, but the soft magnetic characteristics tend to be insufficient. Further, the thermal stability of the amorphous alloy is not sufficient, and there are still unsolved aspects. From the above, the conventional material has a problem that it is difficult to combine high saturation magnetic flux density and excellent soft magnetic characteristics.

From such a background, the present inventors have proposed, as a soft magnetic alloy capable of solving the above-mentioned problems, Japanese Patent Laid-Open No. 5-93.
No. 249, JP-A-4-333546, and Japanese Patent Application No. 3-78.
No. 613, Japanese Patent Application No. 3-78614, Japanese Patent Application No. 5-190
In a patent application such as 674, a patent application for an Fe-B based amorphous soft magnetic alloy produced by a liquid quenching method is filed.
The alloys according to these patent applications are a mixture of an amorphous phase and a fine crystalline phase, and have excellent soft magnetic characteristics, high saturation magnetic flux density and high hardness. However, since the soft magnetic alloy obtained by the liquid quenching method is a ribbon when manufactured, it is difficult to process it in order to use it as the core of the magnetic head or the magnetic core of the pulse motor. There was a problem.

Therefore, the inventors of the present invention consider the application of the soft magnetic alloy, which has been applied for a patent, to the core of the magnetic head, the magnetic core of the pulse motor, the core of the transformer, etc. As a result of various attempts to form into a desired shape by pressing after powdering, a technique enabling the production of a compact of the soft magnetic alloy by a method applying an extrusion molding method has been completed. Regarding the technology, we have previously filed a patent application in Japanese Patent Application No. 6-11980. However, a compact manufactured using this type of soft magnetic alloy exhibits excellent saturation magnetic flux density and excellent magnetic permeability in the middle and low frequency regions, but has low electric resistance, so eddy currents in the high frequency region are high. There is a problem that the loss is large and the magnetic permeability in the high frequency region is not sufficient.

Further, since the soft magnetic alloy according to the above patent has a fine crystal structure obtained by heat-treating an amorphous material, the amorphous magnetic powder formed by the liquid quenching method is In order to produce soft magnetic alloys with various microstructures, compaction molding was performed while maintaining the amorphous state, and a heat treatment was applied to obtain a fine crystalline structure, and amorphous powder was crystallized by heat treatment. A method of consolidating later can be considered. However, when solidified by a method such as hot pressing, if compaction is performed while maintaining the amorphous state and a fine structure is realized by subsequent heat treatment, the density of the obtained compact is not high. There is a problem, and when the powder crystallized by heat treatment is consolidated, there is a problem that a good molding state cannot be obtained.

On the other hand, in addition to the soft magnetic alloy of the composition type for which the present inventors have applied for a patent, a soft magnetic alloy having a structure for precipitating fine crystal grains of nm order is disclosed in Japanese Patent Publication No. 4-43.
As disclosed in No. 93, Fe-Cu-Si-based alloys containing Fe, Cu, and Si as essential elements are known. In any of the soft-magnetic alloys, nano-scale fine crystals are also known. In the case where a compact having a structure is used as a compact, it is important to obtain a uniform structure, and there is a problem that the soft magnetic characteristics of the compact are greatly affected by the uniformity of the structure.

[0008] Further, generally used powder molding methods include hot pressing, extrusion molding, hot isostatic pressing (HIP) and the like. Sintering and extrusion must be done at temperature. In addition, in order to solidify and mold such a powder material at a low temperature, a method of adhering it through an adhesive such as a resin may be considered, but this method cannot increase the molding density and also increases the material strength. There is a problem that cannot be done.

The present invention has been made in view of the above circumstances, and a bulk-shaped soft magnetic alloy compact having excellent magnetic permeability in the middle and low frequency range or high frequency range and having a high saturation magnetic flux density. It is an object of the present invention to provide a manufacturing method thereof and a coating powder for forming the soft magnetic alloy compact.

[0010]

In order to solve the above-mentioned problems, the invention according to claim 1 always contains Fe and at least one of Co and Ni, and further comprises Ti, Zr, Hf,
Alloy grains containing one or more elements selected from V, Nb, Ta, Mo, W, Si, B, and Al, and an inorganic insulator existing in grain boundaries formed around these alloy grains And is provided. In order to solve the above-mentioned problems, the invention according to claim 2 contains Fe and B, and further, Ti,
1 selected from Zr, Hf, V, Nb, Ta, Mo and W
Fe-B based alloy grains containing one or more elements, and an inorganic insulator existing at grain boundaries formed around the alloy grains are provided.

In the above invention, it is preferable that the amorphous phase, the alloy grains, and the structure mainly composed of the inorganic insulator existing in the grain boundaries are used. Further, the inorganic insulator is preferably SiO2. Further, the alloy grains have an average crystal grain size of 30 n.
It is preferable that at least 50% or more of the fine crystalline phase having a bcc structure mainly composed of Fe of m or less is provided with an amorphous phase.

In order to solve the above-mentioned problems, the invention according to claim 6 always contains Fe and at least one of Co and Ni, and further comprises Ti, Zr, Hf, V, Nb, Ta and M.
Amorphous alloy powder containing one or more elements M selected from o, W, Si, B and Al is crystallized at the same time as solidification molding. In order to solve the above-mentioned problems, the invention according to claim 7 contains Fe and B, and one or more selected from Ti, Zr, Hf, V, Nb, Ta, Mo and W. Fe-comprising the elements
The B-based amorphous alloy powder is crystallized at the same time as solidification and molding.

In order to solve the above problems, the present invention contains Fe and B, and further comprises Ti, Zr, Hf,
Fe-B amorphous alloy powder containing one or more elements selected from V, Nb, Ta, Mo, and W and prepared by a liquid quenching method is pressed and heat treated. Are simultaneously applied to form a compact having an average crystal grain size of 30 nm or less and a fine crystal phase mainly composed of Fe and having a bcc structure. In order to solve the above-mentioned problems, the invention according to claim 9 simultaneously performs pressure molding and heat treatment on the Fe-B based amorphous alloy powder according to claim 8 by hot pressing.

In order to solve the above-mentioned problems, the invention according to claim 10 always contains Fe and at least one of Co and Ni, and further Ti, Zr, Hf, V, Nb and T.
Amorphous alloy powder containing one or more elements M selected from a, Mo, W, Si, B, and Al is coated with constituent elements of an inorganic insulating material, and pressure molding is performed on the coating powder. And heat treatment are performed at the same time. Claim 1
In order to solve the above-mentioned problems, the invention according to 1 contains Fe and B, and further comprises Ti, Zr, Hf, V, Nb, Ta,
A Fe-B alloy powder containing one or more elements selected from Mo and W is coated with constituent elements of an inorganic insulator, and the coating powder is subjected to pressure molding and heat treatment at the same time. It is a thing. In order to solve the above-mentioned problems, the invention according to claim 12 immerses the Fe-B based alloy powder in a solution containing the constituent elements of the above-mentioned inorganic insulator, and then dries the alloy powder to form an alloy powder. Is coated with a constituent element of an inorganic insulator.

The inorganic insulator may be SiO2. Further, the heat treatment temperature can be set in the range of 400 to 750 ° C. Further, the above solution may be an alcohol solution of an alkoxide containing a constituent element of an insulator. Furthermore, it is preferable that the Fe-B alloy powder has a particle size of 53 to 100 [mu] m.

In order to solve the above-mentioned problems, the invention as set forth in claim 17 contains Fe and at least one of Co and Ni, and further comprises Ti, Zr, Hf, V, Nb, Ta, Mo,
This is obtained by applying an inorganic insulator coating to an Fe-based amorphous alloy powder containing one or more elements selected from W, Si, B and Al. In order to solve the above-mentioned problems, the invention according to claim 18 contains Fe and B, and further comprises Ti, Zr, Hf, V, Nb, Ta, Mo,
An Fe-B type amorphous alloy powder containing one or more elements selected from W is coated with an inorganic insulator. In order to solve the above-mentioned problems, the invention according to claim 19 coats the coating with SiO2.
It is what

[0017]

Function: Must contain at least one of Fe and Co, and further include Ti, Zr, Hf, V, Nb, Ta, Mo, W, Si,
The alloy grain comprises an alloy grain containing one or more elements selected from B and Al, and an inorganic insulator existing at a grain boundary formed around the alloy grain, or Fe- B
An alloy grain having a composition in which one or more elements selected from Ti, Zr, Hf, V, Nb, Ta, Mo, and W are added to the system, and an inorganic insulator existing at a grain boundary are provided. As a result, the alloy grains containing the above-mentioned elements provide high saturation magnetic flux density and low coercive force, and the inorganic insulator existing at the grain boundaries increases the overall resistance, reducing eddy current loss in the high frequency range. . Therefore, the magnetic permeability in the high frequency region becomes high. SiO2 can be preferably selected as the inorganic insulator. If it is SiO2, it is well compatible with the metal element and can be vitrified by heat treatment for precipitating the Fe-B type fine crystal phase to form an insulator. As the alloy particles, fine crystal grains of a composition system in which Fe or Co contains the above-mentioned elements, or a fine crystal phase of Fe-B system or an amorphous phase containing this fine crystal phase is used to obtain high saturation. A magnetic flux density, a low coercive force, and a high magnetic permeability in the middle and low frequency regions can be secured.

It always contains at least one of Fe and Co, and further contains Ti, Zr, Hf, V, Nb, Ta, Mo, W and S.
One or more elements M selected from i, B and Al
If the amorphous alloy powder containing is crystallized at the same time as solidification molding, the softening phenomenon that occurs when the amorphous phase is crystallized can be used to obtain a good compact having a high compaction density. It is possible to obtain a consolidated body having the desired soft magnetic characteristics. In addition, Fe, B, Ti, Zr, Hf, V, N
If an amorphous alloy powder having a composition containing one or more elements selected from b, Ta, Mo and W is subjected to pressure molding and heat treatment at the same time, the amorphous phase is crystallized. By utilizing the softening phenomenon that occurs at the time of forming, it is possible to obtain a good compact having a high compaction density, and it is possible to obtain a compact having the desired soft magnetic characteristics. In addition, by performing the pressure molding and the heat treatment by hot pressing, the pressure molding and the heat treatment can be performed at the same time, and thus a compact having excellent soft magnetic characteristics can be obtained.

It always contains at least one of Fe and Co, and further contains Ti, Zr, Hf, V, Nb, Ta, Mo, W and S.
One or more elements M selected from i, B and Al
Or Fe-B system containing Ti, Zr, Hf, V, N
Amorphous alloy powder having a composition of a system in which one or more elements selected from b, Ta, Mo, and W are added is coated with constituent elements of an inorganic insulator, and heat-treated under pressure. Therefore, it is possible to easily obtain a consolidated body having an inorganic insulator at the grain boundary. Also, since the coating is only on the outer surface of the alloy grain, the content of the inorganic insulating material in the entire structure can be minimized, and the deterioration of the soft magnetic properties and the decrease of the saturation magnetization due to the addition of the inorganic insulating material are minimized. Become.

The amorphous alloy powder can be coated with the constituent elements of the inorganic insulating material by immersing the amorphous alloy powder in a solution containing the constituent elements of the inorganic insulating material and then drying. Moreover, the thickness of the coating can be adjusted by the content of the inorganic insulating constituent element in the solution. The solution may be an alcohol solution of an alkoxide of a constituent element of the inorganic insulator. The particle size of the alloy powder used is 5
The range of 3 to 150 μm is preferable.

The present invention will be described in more detail below. In order to manufacture the soft magnetic alloy compact according to the present invention, an Fe-B type amorphous alloy having a predetermined composition described later, an amorphous alloy containing some crystal phase, or Fe or Co described later is used. A step of rapidly cooling the amorphous alloy to which the element is added from the molten metal in the form of a ribbon or powder, and pulverizing the ribbon, leaving the powder as it is, such as a hot press described later. It is usually obtained by going through a process of pressure heat treatment. The method for obtaining an amorphous alloy or an amorphous alloy containing some crystalline phase from the molten metal may be a method in which the molten metal is sprayed onto a rotating drum to quench it, or the molten metal is jetted into a cooling gas to quench it. It is also possible to use an atomizing method or the like for pulverizing the powder.

The amorphous alloy or the crystalline alloy containing an amorphous phase used in the present invention has been previously described by the present inventors in JP-A-5-93249, JP-A-4-333546, and Japanese Patent Application No. 3-33. These are disclosed in patent applications such as Japanese Patent Application No. 78613, Japanese Patent Application No. 3-78614 and Japanese Patent Application No. 5-190674. In addition to the above, an alloy of a composition system in which a special additive element is added to Fe or Co described later may be used. The composition examples of the amorphous alloys of the system to which the present inventors have previously applied for a patent or the crystalline alloys containing an amorphous phase and the reasons why it is preferable to have such a composition will be described below. Composition Example 1 A composition having the composition represented by the following formula. Fe b B x My, where M is Ti, Zr, Hf, V, Nb, Ta, M
one or more elements selected from the group consisting of o and W, and containing either or both of Zr and Hf, b = 75 to 93 atom%, x = 0.5 to 18 Atomic%, y
= 4 to 9 atom%.

Composition Example 2 A composition having the composition represented by the following formula. Fe b B x My
X u where M is Ti, Zr, Hf, V, Nb, Ta, M
is one or more elements selected from the group consisting of o and W, and contains one or both of Zr and Hf, and X is selected from the group consisting of Cr, Ru, Rh, and Ir. 1 or 2 or more elements, b = 75 to 93
Atomic%, x = 0.5 to 18 atomic%, y = 4 to 9 atomic%, u ≦
It is 5 atom%.

Composition Example 3 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x My, where Z is either Co or Ni, or both, and M is Ti, Zr, Hf, V, Nb, Ta, Mo, W
One or more elements selected from the group consisting of and containing either or both of Zr and Hf,
a ≦ 0.1, b = 75 to 93 atom%, x = 0.5 to 18 atom%, and y = 4 to 9 atom%.

Composition Example 4 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x My X u where Z is either Co or Ni, or both, and M is Ti, Zr, Hf, V, Nb, Ta, Mo, W
One or more elements selected from the group consisting of and containing either or both of Zr and Hf,
X is 1 selected from the group consisting of Cr, Ru, Rh, and Ir.
Or two or more kinds of elements, a ≦ 0.1, b = 75 to
93 atomic%, x = 0.5 to 18 atomic%, y = 4 to 9 atomic%, and u ≦ 5 atomic%.

Composition Example 5 A composition having the composition represented by the following formula. Fe b B x M '
y However, M ′ is one or more elements selected from the group consisting of Ti, V, Nb, Ta, Mo and W, and contains Nb, and b = 75 to 93 atom%, x = 6.5-1
8 atomic% and y = 4 to 9 atomic%.

Composition Example 6 A composition having the composition represented by the following formula. Fe b B x M '
y X u where M ′ is one or more elements selected from the group consisting of Ti, V, Nb, Ta, Mo and W, and contains Nb, and X is Cr, Ru, One or more elements selected from the group consisting of Rh and Ir, and b =
75-93 atom%, x = 6.5-18 atom%, y = 4-9
Atomic% and u ≦ 5 atomic%.

Composition Example 7 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x M'y where Z is either Co or Ni, or both and M'is one or two selected from the group consisting of Ti, V, Nb, Ta, Mo and W. The above elements, and
Including Nb, a ≦ 0.1, b = 75 to 93 atom%, x = 6.
It is 5-18 atomic% and y = 4-9 atomic%.

Composition Example 8 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x M'y X u where Z is Co or Ni, or both, and M'is one or more selected from the group consisting of Ti, V, Nb, Ta, Mo and W or Two or more elements, and
Including Nb, X is one or more elements selected from the group consisting of Cr, Ru, Rh, and Ir, and a ≦ 0.
1, b = 75 to 93 atom%, x = 6.5 to 18 atom%, y =
4 to 9 atomic%, u ≦ 5 atomic%.

Composition Example 9 A composition having the composition represented by the following formula. Fe b B x M
y T z However, M is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains either or both of Zr and Hf, and T is Cu, Ag, Au, Pd, Pt, or Bi. One or more elements selected from the group consisting of
b ≦ 75 to 93 atom%, x = 0.5 to 18 atom%, y = 4 to
10 atomic% and z ≦ 4.5 atomic%.

Composition Example 10 A composition having the composition represented by the following formula. Fe b B x My
T z X u where M is Ti, Zr, Hf, V, Nb, Ta, M
One or two or more elements selected from the group consisting of o and W, and contains either or both of Zr and Hf, and T is Cu, Ag, Au, Pd, Pt, or Bi. One or more elements selected from the group consisting of
X is 1 selected from the group consisting of Cr, Ru, Rh, and Ir.
One or two or more elements, b ≦ 75 to 93 atom%, x = 0.5 to 18 atom%, y = 4 to 10 atom%, z ≦
It is 4.5 atomic%, u ≦ 5 atomic%.

Composition Example 11 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x My T z However, Z is either Co or Ni, or both,
M is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W, and
And includes either or both of Zr and Hf, and T
Is one or more elements selected from the group consisting of Cu, Ag, Au, Pd, Pt and Bi, and a ≦ 0.1,
b ≦ 75 to 93 atom%, x = 0.5 to 18 atom%, y = 4 to
10 atomic% and z ≦ 4.5 atomic%.

Composition Example 12 A composition having the composition represented by the following formula. (Fe 1-a Z a) b
B x My T z X u However, Z is either Co or Ni, or both,
M is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo and W, and
And includes either or both of Zr and Hf, and T
Is one or more elements selected from the group consisting of Cu, Ag, Au, Pd, Pt and Bi, and X is Cr,
1 or 2 selected from the group consisting of Ru, Rh and Ir
More than one element, a ≦ 0.1, b ≦ 75 to 93 atom%, x = 0.5 to 18 atom%, y = 4 to 10 atom%, z ≦
It is 4.5 atomic%, u ≦ 5 atomic%.

Composition Example 13 A composition having the composition represented by the following formula. Fe b B x M '
y T z However, M ′ is one or more elements selected from the group consisting of Ti, V, Nb, Ta, Mo and W, and contains any one of Ti, Nb and Ta. , T is Cu,
One or more elements selected from the group consisting of Ag, Au, Pd, Pt, and Bi, and b ≦ 75 to 93 atom%, x = 6.5 to 18 atom%, y = 4 to 10 Atomic%, z ≦
It is 4.5 atomic%.

Composition Example 14 A composition having the composition represented by the following formula. Fe b B x M '
yT z X u where M ′ is one or more elements selected from the group consisting of Ti, V, Nb, Ta, Mo and W, and is any one of Ti, Nb and Ta. , T is Cu,
One or more elements selected from the group consisting of Ag, Au, Pd, Pt, Bi, and X is Cr, Ru, R
one or more elements selected from the group consisting of h and Ir, b ≦ 75 to 93 atom%, x = 6.5 to 18 atom%, y = 4 to 10 atom%, z ≦ 4 0.5 atomic% and u ≦ 5 atomic%.

Composition Example 15 A composition having the composition represented by the following formula. (Fe 1-a Z
a) b B x M'y T z However, Z is either or both of Co and Ni,
M'is one or more elements selected from the group consisting of Ti, V, Nb, Ta, Mo and W, and Ti,
Containing either Nb or Ta, T is Cu, Ag, Au,
1 or 2 selected from the group consisting of Pd, Pt and Bi
More than one element, a ≦ 0.1, b ≦ 75 to 93 atom%, x = 6.5 to 18 atom%, y = 4 to 10 atom%, z ≦
It is 4.5 atomic%.

Composition Example 16 A composition having the composition represented by the following formula. (Fe 1-a Z a) b
B x M'y T z X u where Z is either or both of Co and Ni, and M'is one selected from the group consisting of Ti, V, Nb, Ta, Mo and W, or Two or more elements, and
It contains any one of Ti, Nb and Ta, and T is Cu, Ag,
One or more elements selected from the group consisting of Au, Pd, Pt and Bi, and X is Cr, Ru, Rh, I.
1 or 2 or more elements selected from the group consisting of r, a ≦ 0.1, b ≦ 75 to 93 atom%, x = 6.5 to 1
8 atom%, y = 4 to 10 atom%, z ≦ 4.5 atom%, u ≦ 5
It is atomic%.

Composition Example 17 In the Fe-based soft magnetic alloy described in Composition Examples 1 to 16, z = 0.2 to 4.5 atomic%.

B is inevitably added to the soft magnetic alloys having the compositions shown in Composition Examples 1 to 17. For B, the effect of increasing the amorphous forming ability of the soft magnetic alloy, Fe-M (= Zr, Hf, N
b)) has an effect of increasing the thermal stability of the microcrystalline alloy and can be a barrier to the growth of crystal grains, and an effect of leaving a thermally stable amorphous phase at the grain boundaries. As a result, it is possible to obtain a structure mainly composed of fine crystal grains having a body-centered cubic structure (bcc structure) having a grain size of 30 nm or less that does not adversely affect the magnetic properties under a wide heat treatment condition of 400 to 750 ° C. in the heat treatment step. it can. Like B, A1, Si, C, P and the like are generally used as amorphous forming elements, and the addition of these elements can be regarded as the same as the present invention. The heat treatment temperature is more preferably in the range of 500 to 650 ° C. in order to obtain an alloy having particularly excellent soft magnetic characteristics.

In the soft magnetic alloys of the inventions of Composition Examples 1 to 4 and 9 to 12, in order to easily obtain an amorphous phase, it is necessary to contain either Zr or Hf having a high amorphous forming ability. .
In addition, Zr and Hf are partially included in other periodic rate tables 4A to 6A.
Among the group elements, Ti, V, Nb, Ta, Mo and W can be substituted. In this case, the amount of B is 0.5 to 10 atom%, or when the element T is contained, the amount of B is 0.5 to 1
By setting the content to 8 atomic%, it is possible to obtain a sufficient amorphous forming ability. Further, magnetostriction can be reduced by solid-solving Zr and Hf, which are elements that are not originally solid-dissolved in Fe. That is, the solid solution amounts of Zr and Hf can be adjusted under the heat treatment conditions, whereby the magnetostriction can be adjusted and the value thereof can be reduced. Therefore, in order to obtain a low magnetostriction, it is necessary to obtain a fine crystal structure under a wide heat treatment condition, and as described above, addition of B makes it impossible to obtain a fine crystal structure under a wide heat treatment condition. It has both magnetostriction and small crystal magnetic anisotropy, and as a result, it has good magnetic characteristics.

Further, in the above composition, Cr, Ru, Rh and Ir are added.
Although the corrosion resistance is improved by adding as necessary, it is necessary to add 5 elements or less of these elements in order to maintain the saturation magnetic flux density at 10 kG or more.

In 1980, the present inventors found that a fine crystal structure can be obtained by partially crystallizing an Fe-M (= Zr, Hf) type amorphous alloy by a special method. METALLIC SCIENCE AND TECHNOLGY
BUDAPEST ", pages 217-221. Subsequent studies have revealed that the composition disclosed this time has the same effect. As a result, the present invention has been achieved. The reason why this fine crystal structure can be obtained is that an alloy of this system is produced. It is considered that composition fluctuation has already occurred in the rapid cooling state at the stage of forming the amorphous phase for this purpose, and this fluctuation becomes a site of heterogeneous nucleation, and many uniform and fine nuclei are generated.

In the soft magnetic alloys of the invention described in Composition Examples 1 to 16, the Fe content or the Fe, Co and Ni contents are 93 atomic% or less. This is because if the content of these exceeds 93 atom%, a high magnetic permeability cannot be obtained, but in order to obtain a saturation magnetic flux density of 10 kG or more, it is more preferably 75 atom% or more.

In the soft magnetic alloys of the inventions of Composition Examples 9 to 16, at least one selected from Cu and Ag and Au of the elements homologous to Cu and Pd, Pt and Bi.
It is preferable to contain 4.5 atomic% or less of one element or two or more elements. If the added amount of these elements is less than 0.2 atomic%, it becomes difficult to obtain excellent soft magnetic characteristics by the heat treatment step, but the permeability is improved and the saturation magnetic flux density is increased by increasing the heating rate. Since it is slightly improved, the content of these elements may be 0.2 atomic% or less as shown in Composition Examples 9 to 16. However, by setting the contents of these elements to 0.2 to 4.5 atomic%, excellent soft magnetic characteristics can be obtained without increasing the temperature rising rate too much. It is more preferable to set the content to 0.2 to 4.5 atomic%.

Among these elements, Cu is particularly effective. Although the mechanism by which addition of Cu, Pd, etc. significantly improves the soft magnetic properties is not clear, the crystallization temperature was measured by a differential thermal analysis method.
It was confirmed that the crystallization temperature of the alloy to which Cu, Pd, etc. were added was slightly lower than that of the alloy to which it was not added.
It is considered that this is because the compositional fluctuation in the amorphous phase was increased by the addition of the above elements, and as a result, the stability of the amorphous phase was lowered and the crystalline phase was easily precipitated.

Further, when the heterogeneous amorphous phase is crystallized, a large number of regions which are likely to be partially crystallized and heterogeneous nucleation is generated, and the obtained structure becomes a fine crystal grain structure, which is excellent. Magnetic properties are obtained. Furthermore, if the temperature raising rate is increased, finer crystallinity is promoted. Therefore, when the temperature raising rate is high, elements such as Cu and Pd may be contained in less than 0.2 atom%. . Further, particularly in the case of Cu, which is an element whose solid solubility in Fe is extremely low, there is a tendency for phase separation, and therefore microscopic composition fluctuations occur due to heating, and the tendency for the amorphous phase to become nonuniform becomes more pronounced. It is considered that this is considered to contribute to the refinement of the structure. From the above viewpoints, Cu and its homologous elements, P
Similar effects can be expected for elements other than d and Pt that lower the crystallization temperature. In addition to Cu, similar effects can be expected for elements such as Bi having a small solid solubility limit with respect to Fe.

In order to easily obtain an amorphous phase in the soft magnetic alloys of Composition Examples 5 to 8 and 13 to 16, it is necessary to contain Nb and B having an amorphous forming ability. Ti, V, T
Although a, Mo, and W have the same effect as Nb, V, Nb, and Mo among these elements have a relatively small oxide formation tendency, and a good yield can be obtained during manufacturing.
Therefore, when these elements are added, the manufacturing conditions are relaxed, the manufacturing cost is low, and the cost is also advantageous. Specifically, it can be manufactured in the atmosphere or in the atmosphere while partially supplying an inert gas to the tip of the nozzle. However, since these elements are inferior to Zr and Hf in terms of the amorphous forming ability, the B content is increased in the soft magnetic alloys of Composition Examples 6 to 8 and 13 to 16, and the lower limit value is set. It was set to 6.5 atom%.

The reasons for limiting the alloying elements contained in the soft magnetic alloy of the present invention have been described above. If necessary, Y, rare earth elements, Zn, Cd, Ga, In, Ge, Sn, Pb,
As, Sb, Bi, Se, Te, Li, Be, Mg, C
Magnetostriction can also be adjusted by adding elements such as a, Sr, and Ba. In addition, inevitable impurities such as H, N, O, and S can be regarded as the same as the composition of the Fe-B alloy according to the present invention even if they are contained to the extent that the desired characteristics are not deteriorated. Of course.

In addition to the composition system for which the present inventors have applied for a patent, an Fe-based soft magnetic alloy having a high magnetic permeability and a saturated magnetic flux density, and capable of exhibiting a fine crystal structure. , (Fe1-dZd) 100-efg-hCueSifBgAh. (See Japanese Patent Publication No. 4-4393) (where Z is Co or Ni, or both,
A is at least one element selected from the group consisting of Nb, W, Ta, Zr, Hf, Ti and Mo, and d, e, f, g, h
Are 0 ≦ d ≦ 0.5, 0.1 ≦ e ≦ 3, 0 ≦ f ≦, respectively.
30, 5 ≦ e + f ≦ 30, and 0.1 ≦ h ≦ 30 are satisfied. Therefore, the amorphous alloy powder of the soft magnetic alloy of this system can be used for the step described later.

An example of the method for producing a compact according to the present invention will be described in detail below. Once the raw materials are weighed and mixed so that the composition of each of the above composition examples is obtained, they are vacuum-melted or arc-melted to prepare an ingot, which is melted in a crucible, and at the same time, a spout formed at the tip of the crucible From the holes, the molten metal is sprayed together with the carrier gas onto the surface of a rotating metal roll such as a copper roll and rapidly cooled to obtain a ribbon-shaped (ribbon-shaped) amorphous alloy or an amorphous alloy containing some crystal phase. . Next, the obtained alloy ribbon is crushed by a crushing machine such as a rotor speed mill or a planetary ball mill to obtain a crushed product. The obtained pulverized product has a particle size of 50 μm or less and a particle size of 50 to 1 using a mesh.
Classify into those with a particle size of 50 μm and particles with a particle size above 150 μm.

The particle size of 50 is used in the following steps.
The powder is classified to have a size of at least μm. If the particle size of the powder is too small, there is a high possibility that a metal material such as stainless steel forming a blade of a crushing machine is mixed therein, which is not preferable. That is, since the amorphous alloy having the above composition is hard, when it is crushed, it is separated by abrasion of a part of the blade of the crushing machine or a part rubbed with the amorphous alloy, and the separated product is crushed. May get mixed in things. At the same time, it is considered that the powder having a small particle size is considered to have its amorphous phase portion changed to a crystalline phase due to the mechanical action at the time of grinding and frictional heating, and therefore it is preferably removed. Although the above classification work is performed to remove impurities which are considered to be contained when the thin strip is crushed, it was possible to obtain an amorphous alloy powder containing no impurities by the atomization method or the like. In that case, the powder may be used as it is in the following steps without classification.

After the powder is prepared, it is coated with an insulating film. Various methods are conceivable for forming the insulating film, such as a method of forming an insulating film using a sol-gel method, a method of spray-coating a solution containing an insulating material, drying, and low-temperature firing. In this example, a method using the sol-gel method will be described. In order to form an insulating film, a solution is prepared by dissolving an element constituting an inorganic insulating material such as SiO2, ZrO2, and TiO2 and an alkoxide, which is a salt of an alkoxy group, in an organic solvent such as alcohol, and forming the powder into the solution. Is dipped, and then the powder pulled out of the solution is dried. By this treatment, the coating powder 3 having the cross-sectional structure as shown in FIG. 1 and having the surface of the powder 2 uniformly coated with the coating 1 having a thickness of submicron order can be manufactured. The thickness of the coating 1 can be adjusted according to the concentration of the alkoxide dissolved in the solution. Therefore, it is possible to control the amount of the inorganic insulator contained in the compacted body produced by compacting the coating powder 3 as described later by adjusting the concentration of the solution.

Next, apply the coating powder 3 to the piston
400 to 75 by vacuum hot press such as cylinder method
While being heated to a temperature of 0 ° C., it is held for a predetermined time and molded into a desired shape. The heating temperature at this time is appropriately adjusted according to the composition of the soft magnetic alloy to be generated, but in order to obtain a soft magnetic alloy compact having higher soft magnetic characteristics, 500
It is preferable to heat in the range of ˜650 ° C. By this pressure heat treatment, the amorphous phase or the powder 3 mainly composed of the amorphous phase is consolidated, and at the same time, the Fe—B-based fine crystalline phase is precipitated in the amorphous phase. This fine crystal phase is fine with an average crystal grain size of 30 nm or less. In addition, the coating 1 of the insulating material coated on the outer surface of each powder is Fe-
The B-based amorphous phase or the Fe-B-based fine crystalline phase aggregates to precipitate at the grain boundaries of the alloy grains, and the overall structure after consolidation is the alloy grains and the insulation that precipitates at the grain boundaries. It exhibits a structure consisting of physical layers. Coating 1 of the composition is 500
Since it becomes glass at ˜600 ° C., it can be easily deposited as an insulating layer by heat treatment at the above temperature. Further, if it is an insulating layer of SiO2, it has good compatibility with metals and excellent bondability between alloy particles. Therefore, the strength of the compact is also improved.

The compact having the above-mentioned structure is Fe
Since a Co-based, FeNi-based, or Fe-B-based fine crystalline phase is deposited, the saturation magnetic flux density is high, the magnetic permeability is excellent, and the coercive force is low. In addition, since SiO2, which is an insulator, is deposited on the grain boundaries of the alloy grains, the specific resistance of the entire structure is high. Therefore, an eddy current loss in the high frequency region is small, and a compact having a high magnetic permeability in the high frequency region can be obtained. Therefore, this compact body can be widely applied as a core of a magnetic head, a core of a transformer, or a magnetic component such as a magnetic needle of a pulse motor, etc., and a magnetic component having superior characteristics to conventional materials. Can be obtained.

Further, according to the above-mentioned manufacturing method, since the consolidation and the precipitation of the fine crystal phase are simultaneously performed by using the method called hot pressing, it is possible to utilize the softening phenomenon of the alloy accompanying the crystallization. It is possible to realize a high molding density. On the other hand, a sufficient compacting density cannot be obtained by the method in which the amorphous phase powder is once crystallized and then consolidated, and the method in which the amorphous phase powder is consolidated and then heat-treated to crystallize. . If such a method of simultaneously compacting powder and performing heat treatment is adopted, an alloy having a high compaction density can be obtained, and at the same time, the saturation magnetization of the alloy also becomes high.

By the way, in the above-mentioned example, although the compact was manufactured by using the amorphous powder coated with the insulating material and the compact having excellent high frequency characteristics was manufactured, the transformer used in the middle and low frequency regions is used. When used for a magnetic core, a powder not coated with an insulating material may be pressed with a hot press and heated at the same time to form a compact. This treatment also makes it possible to obtain a compact having a high saturation magnetic flux density and a high magnetic permeability in the middle and low frequency regions.

When the amorphous phase is consolidated by utilizing the softening phenomenon that occurs during crystallization, a powder of the amorphous phase is prepared and solidified and simultaneously crystallized to cause a softening reaction. It is possible to perform compaction molding. Therefore, if this method is used, in addition to the composition system described above, Fe-Al-
Even sendust alloys known as Si-based alloys can be consolidated. In this Sendust alloy, S
Since there is a component that can be made amorphous by increasing i and adjusting the Al content, it is possible to make an amorphous alloy by this, and according to this method, amorphized Fe is used. -
By compacting by utilizing the softening phenomenon of the Al-Si alloy powder, it becomes possible to obtain a dense compact of the Fe-Al-Si alloy.

[0058]

【Example】

(Example 1) The raw materials were weighed and mixed so as to have a composition of Fe86Zr7B6Cu1 and arc-melted to prepare an ingot, which was melted in a crucible and sprayed from a crucible nozzle onto a rotating roll by a liquid quenching method. A plurality of amorphous alloy ribbon samples were obtained. In the liquid quenching method, the atmosphere argon gas pressure was set to 36 to 56 cmHg, the rotation speed of the copper roll was set to 2500 to 3000 rpm, and the argon ejection pressure was set to 0.1 to 1 kg / cm <2>, respectively, to prepare each sample.

Further, the obtained amorphous alloy ribbon sample (ribbon) was pulverized by a planetary ball mill at a liquid nitrogen temperature and pulverized. The obtained pulverized product has a particle size of 50 with a mesh.
Particle sizes of 50 to 100 μm, particles of 50 to 100 μm, and particles of 100 μm or more.
The thing of m was used for the test. A schematic of an electron micrograph of this powder is shown in FIG. Next, a powder of this particle size is treated with an organosilicon compound, methanol "Nitso Kasei Co., Ltd., trade name Atron: R.
-O (SiO2) "was immersed in a solution of alcohol solution. When the powder was taken out of the solution and dried at 200 ° C., a coating powder covered with a silica gel film having a thickness of 0.4 μm could be obtained.

Using the above coating powder, as shown in FIG. 3, consolidation was performed by a piston-cylinder method using a vacuum hot press. In FIG. 3, reference numeral 10 is a cemented carbide cylinder, 11 is a cemented carbide upper piston inserted in the cylinder 10, 12 is a cemented carbide lower piston, 13 is powder, and 14 is a thermocouple. Is. An example of the temperature and pressure in the case of consolidating with this device is 0.33 ° C. under a pressure of 1.5 GPa as shown in FIG.
The temperature was raised to 580 ° C. at a speed of / s and pressure was maintained for 200 seconds. FIG. 5 shows a schematic view of a SEM (scanning electron microscope) photograph (400 times) of the structure of the obtained compact. It was possible to confirm the existence of the alloy grains 5 mainly composed of the Fe-B-based fine crystal phase and the insulator 6 made of SiO2 existing in the grain boundaries around the alloy grains. Next, FIG. 6 shows the Si surface analysis result (electron probe micro analysis method result) of the tissue of the same portion of the same compact. In this figure, the black dots are SiO2
However, it is clear that SiO2 is particularly concentrated and deposited on the grain boundaries of the alloy grains to form an insulating film. Further, FIG. 7 shows the structure state of the alloy grain portion of the consolidated body by a transmission electron micrograph. The fine crystalline phase (average crystal grain size of 30 nm) shown in a black region having a grain size smaller than 1000 angstrom (= 100 nm). It is clear that the following) are deposited.

The magnetic properties of the obtained compact were measured by VSM, DC BH tracer and impedance analyzer. The frequency dependence of the effective permeability of the measurement results is shown in FIG. Further, FIG. 8 shows the frequency dependence of the effective magnetic permeability of the consolidated body manufactured by performing the same hot pressing using the powder on which the silica gel film is not formed. as a result,
The sample using the powder with the silica gel film formed was 0.8 A / m, 1 kH compared to the sample using the powder without the film.
The value of z is slightly less than 1000, which is slightly inferior to the sample in which the silica gel film is not formed.
The effective magnetic permeability in the high frequency region of 0 kHz or higher was reversed by the effect of suppressing the eddy current, and showed a high value of 150 even in the high frequency region of 10 MHz. The saturation magnetization of this sample was 1.53 T (tesla) and the coercive force was 0.57 Oe.

(Example 2) DSC (differential scanning calorimetry) curve and TMA of an alloy having a composition of Fe86Zr7B6Cu1
(Thermo Mechanical Analysis) curve is shown in FIG. It can be seen that the sample softens near the crystallization temperature, and it is desirable to utilize this softening phenomenon to compact the powder. A first method in which an amorphous alloy powder having the same composition and particle diameter as in Example 1 is used, and the amorphous alloy powder is once consolidated into an amorphous state without being coated and then heat-treated, and the coating is performed. A second method in which a non-crystalline alloy powder is heat-treated at the same time as it is consolidated by the same method as in Example 1, and a third method in which the amorphous alloy powder is once heat-treated to be finely crystallized and then consolidated. Perform each method 3
A variety of compact samples were obtained. The pressure applied by the hot press machine used for solidification molding was set to 1.5 GPa in all cases. The finely crystallized alloy powder was produced by heat-treating an amorphous alloy powder in vacuum under heating conditions of 600 kC for 3.6 ks.

Scanning electron microscope photographic images of the samples consolidated by the first, second and third methods are shown in FIG.
Shown in (a), (b) and (c). It can be seen that the sample compacted by the second method shows a better molding state than the samples compacted by the first and third methods. It should be noted that the scattered irregular shapes seen in FIGS. 10 (a) and 10 (c) indicate holes, which means that the consolidation is not perfect, but in FIG. No large pores could be confirmed, indicating that the molding was in a good condition. The maximum density of the compact (outer diameter 4.0 mm, inner diameter 2.0 mm, thickness 1.0 mm) obtained by the first method is 94.5.
%, The maximum density of the compact obtained by the second method is 99.9
%, The maximum density of the compact obtained by the third method is 90.4
%Met. Further, the minimum pressure of each method for obtaining a molded product having a density of 99.9%, which is obtained from the density of the obtained consolidated product and the consolidation condition, is 3.0 GP in the first process.
a, the second method is 1.5 Ga, the third method is 4.4 G
It was Pa. From the above results, it has been clarified that it is effective to perform heat treatment simultaneously with solidification by hot pressing in order to form a high-density fine crystallized alloy by solidification forming.

Next, according to the second method, 1.5 GPa, 5
The saturation magnetization of the compact produced under the condition of 80 ° C. is 600
1.3T to 1.56T by heat treatment at 1.8 ° C for 1.8ks
Rose to. The coercive force of the heat-treated compact is 33 A / m, and the effective magnetic permeability at 1 kHz and 0.8 A / m is 130.
It was 0. The saturation magnetization of the molded body of this fine crystal alloy is
It was equivalent to the Fe-based amorphous compact produced by explosion molding or extrusion molding, and its soft magnetic properties were superior to those of the Fe-based amorphous alloy compact. From the above, it has been clarified that the compact body manufactured by the second method has better magnetic characteristics than the one manufactured by the first and third methods. Moreover, the second
If the method is used, it is possible to obtain a compaction density equivalent to that of the explosive molding which is considered to have the highest compaction density.

Further, Fe73.5Cu1Nb3Si13.5B
9, Fe73.5Cu1Nb3Si16.5B6, Fe71.5Cu1M
o5Si13.5B9, Fe71.5Cu1W5Si13.5B9, Fe7
6Cu1Ta3Si12B8, Fe73Cu1Hf4Si14B8,
(Fe0.95Co0.05) 72Cu1Nb5Si12B10, (Fe
0.85Co0.15) 72Cu1Nb5Si10B12, Fe84Nb7
When a compact was manufactured by the second method in the composition of B9, Fe90Zr7B3, and Fe89Zr7B3Cu1, the density and magnetic characteristics were almost the same as those of the composition in Example 2.

[0066]

As described above, according to the present invention, F
e and at least one of Co and Ni are always included,
Furthermore, Ti, Zr, Hf, V, Nb, Ta, Mo, W,
Alloy particles containing one or more elements selected from Si, B and Al, or Ti, Zr and H in the Fe-B system
Since it is provided with an alloy grain having a composition to which one or more elements selected from f, V, Nb, Ta, Mo and W are added and an inorganic insulator existing at the grain boundary, High saturation magnetic flux density and low coercive force can be obtained by the alloy grains to which the above elements are added. Further, since the inorganic insulator existing at the grain boundaries of the alloy grains can increase the electric resistance of the whole, the eddy current loss in the high frequency region can be reduced and the magnetic permeability in the high frequency region can be increased.

SiO 2 can be preferably used as the inorganic insulator. If it is SiO2, it has good compatibility with metal elements and is vitrified by heat treatment for precipitating a fine crystal phase such as FeCo-based, Fe-Ni-based, or Fe-B-based to form an inorganic insulator. As an alloy grain, F
By using an eCo-based, Fe-Ni-based, or Fe-B-based fine crystalline phase or an amorphous phase containing this fine crystalline phase, a high saturation magnetic flux density, a low coercive force, and a high mid-low frequency region can be obtained. Permeability can be secured.

Further, the method of the present invention always contains at least one of Fe and Co, and further comprises Ti, Zr, Hf, V, N.
Since the amorphous alloy powder containing one or more elements selected from b, Ta, Mo, W, Si, B, and Al is crystallized at the same time as solidification and molding, it proceeds simultaneously with solidification and molding. Since the powder can be efficiently compacted by utilizing the amorphous softening phenomenon described above, it is possible to obtain a compact having a high compaction density and excellent saturation magnetic flux density and soft magnetic characteristics. Furthermore, F
e-B system with Ti, Zr, Hf, V, Nb, Ta, Mo,
Since the amorphous alloy powder having a composition to which one or more elements selected from W are added is subjected to pressure molding and heat treatment at the same time, the amorphous phase of the amorphous alloy powder is changed to the fine crystalline phase. Can be smoothly precipitated and can be processed with the amorphous phase being changed into a crystalline phase other than the fine crystalline phase or a precipitate without being changed as much as possible, so that a consolidated body having desired soft magnetic characteristics can be obtained. Furthermore, by performing the pressure molding and the heat treatment by hot pressing, it is possible to easily perform the pressure molding and the heat treatment at the same time, which allows the amorphous alloy powder to be once crystallized and then consolidated. It is possible to obtain a consolidated body having excellent soft magnetic characteristics as compared with a method in which the crystalline alloy powder is consolidated and then crystallized.

The method of the present invention always contains at least one of Fe and Co, and further comprises Ti, Zr, Hf, V, Nb and T.
Amorphous alloy powder containing one or more elements selected from a, Mo, W, Si, B and Al, or Fe
-Ti, Zr, Hf, V, Nb, Ta, Mo, W for B type
Amorphous alloy powder having a composition to which one or more elements selected from the above are coated with the constituent elements of the inorganic insulator, and these are heat-treated under pressure. It is possible to easily obtain the compacted body having. Further, by coating only the outer surface of the alloy grains, the content of the inorganic insulating material in the entire structure is reduced, and deterioration of the soft magnetic characteristics due to the addition of the inorganic insulating material can be minimized.

On the other hand, the coating of the constituent elements of the inorganic insulator on the amorphous alloy powder can be performed by immersing the amorphous alloy powder in a solution containing the constituent elements of the inorganic insulator and then drying. Moreover, the thickness of the coating can be adjusted by the content of the inorganic insulating constituent element in the solution. Further, the solution can be an alcohol solution of an alkoxide of a constituent element of the inorganic insulator. The grain size of the alloy powder to be used is preferably 53 to 150 μm, and by using the powder in this range, the partially crystallized amorphous alloy powder can be removed. As a result, a fine crystalline phase having a desired crystal structure can be precipitated from the amorphous phase to obtain a compact having a desired soft magnetic characteristic.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of coating powder.

FIG. 2 is a schematic diagram of an electron micrograph showing a particle structure of an example of the coating powder obtained in the example.

FIG. 3 is a cross-sectional view showing an example of a piston / cylinder device used in Examples.

FIG. 4 is a diagram showing an example of manufacturing conditions used in Examples.

FIG. 5 is a schematic view showing a structure of a consolidated body manufactured in an example.

6 is a diagram showing the results of Si surface analysis of the same portion as the structure shown in FIG.

FIG. 7 is a schematic diagram of a transmission electron micrograph of a metal structure of an alloy grain portion of the same consolidated body.

FIG. 8 is a diagram showing the frequency dependence of the effective magnetic permeability of the samples obtained in the examples.

9 (a) is a diagram showing a DSC curve of the sample obtained in the example, and FIG. 9 (b) is a diagram showing a TMA curve of the sample.

10 (a) is a schematic view of a metallographic photograph of a sample obtained by the first method of Example 2, and FIG. 10 (b) is a sample obtained by the second method of Example 2. FIG. 10C is a schematic diagram of a metallographic photograph of the sample obtained by the third method of Example 2.

[Explanation of symbols]

 1 Coating 2 Amorphous alloy powder 3 Coating powder 5 Alloy particles 6 Insulator

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C22C 45/02 A // C22C 38/00 303 S (72) Inventor Akinobu Kojima Ota Ward, Tokyo Yutani Otsuka-cho 1-7 Alps Electric Co., Ltd. (72) Inventor Nomura Kawamura 2-429 Yonegabukuro, Aoba-ku, Sendai-shi, Miyagi Bell City Yonegabukuro 205 (72) Inventor Akihisa Inoue Miyagi 11-806 Kawauchi House, No. Kawauchi, Aoba-ku, Sendai, Japan

Claims (19)

[Claims] 1. Fe and at least one of Co and Ni must be contained, and Ti, Zr, Hf, V, Nb and T are further included.
an alloy grain containing one or more elements selected from a, Mo, W, Si, B, and Al; and an inorganic insulator existing in a grain boundary formed around the alloy grain. A soft magnetic alloy compact body characterized by the following. 2. Fe and B, further comprising Ti, Z
Fe-B alloy grains containing one or more elements selected from r, Hf, V, Nb, Ta, Mo and W and grain boundaries formed around these alloy grains. A soft magnetic alloy compact, comprising an existing inorganic insulator. 3. The soft magnetic alloy compact according to claim 1, comprising an amorphous phase, alloy grains, and a structure mainly composed of an inorganic insulator existing at grain boundaries. 4. The soft magnetic alloy compact according to claim 1, wherein the inorganic insulator is SiO 2. 5. The alloy grain comprises at least 50% or more of a fine crystalline phase having a bcc structure mainly composed of Fe and having an average grain size of 30 nm or less, and an amorphous phase. The soft magnetic alloy compact according to any one of 1 to 4. 6. Fe, and at least one of Co and Ni must be contained, and further Ti, Zr, Hf, V, Nb, T.
Manufacture of a soft magnetic alloy compact, which is characterized in that an amorphous alloy powder containing one or more elements selected from a, Mo, W, Si, B and Al is crystallized simultaneously with solidification molding. Method. 7. Fe and B, further comprising Ti, Z
Fe-B type amorphous alloy powder containing one or more elements selected from r, Hf, V, Nb, Ta, Mo and W is solidified and crystallized at the same time And a method for manufacturing a soft magnetic alloy compact. 8. Fe and B, further comprising Ti, Z
An Fe-B-based amorphous alloy powder containing one or more elements selected from r, Hf, V, Nb, Ta, Mo and W and prepared by a liquid quenching method is added to F with an average crystal grain size of 30 nm or less is obtained by simultaneously performing pressure forming and heat treatment.
A method for producing a soft magnetic alloy compact, which comprises forming a compact having a bcc-structured fine crystalline phase mainly composed of e. 9. The method for producing a soft magnetic alloy compact according to claim 8, wherein pressure molding and heat treatment of the Fe—B based amorphous alloy powder are simultaneously performed by hot pressing. 10. Inevitably containing Fe and at least one of Co and Ni, and further comprising Ti, Zr, Hf, V and N.
Amorphous alloy powder containing one or more elements selected from b, Ta, Mo, W, Si, B and Al is coated with constituent elements of an inorganic insulator, and the coating powder is pressed. A method for manufacturing a soft magnetic alloy compact, which comprises simultaneously performing molding and heat treatment. 11. Fe and B, and further Ti, Z
Fe-B alloy powder containing one or more elements selected from r, Hf, V, Nb, Ta, Mo and W is coated with constituent elements of an inorganic insulator, and this coating is performed. A method for manufacturing a soft magnetic alloy compact, which comprises subjecting powder to pressure molding and heat treatment at the same time. 12. A solution containing a constituent element of an inorganic insulator is F
The soft magnetic alloy compact according to claim 10 or 11, wherein the e-B type alloy powder is dipped, and then the alloy powder is dried to coat the alloy powder with a constituent element of an inorganic insulator. Production method. 13. The method for manufacturing a soft magnetic alloy compact according to claim 12, wherein the inorganic insulator is SiO 2. 14. The method for producing a soft magnetic alloy compact according to claim 8, wherein the heat treatment temperature is in the range of 400 to 750 ° C. 15. The method for producing a soft magnetic alloy compact according to claim 12, wherein the solution is an alcohol solution of an alkoxide containing a constituent element of an insulator. 16. The method for producing a soft magnetic alloy compact according to claim 10, wherein the particle size of the powder is 53 to 100 μm. 17. Fe, at least one of Co and Ni, and further Ti, Zr, Hf, V, Nb and T.
A Fe-based amorphous alloy powder containing one or more elements selected from a, Mo, W, Si, B, and Al is coated with an inorganic insulator. Coating powder for forming soft magnetic alloy compacts. 18. Fe and B, and further Ti, Z
Fe-B based amorphous alloy powder containing one or more elements selected from r, Hf, V, Nb, Ta, Mo and W, coated with an inorganic insulator. A coating powder for forming a soft magnetic alloy compact, characterized by: 19. The coating powder for forming a soft magnetic alloy compact according to claim 17, wherein the coating is SiO 2.