JPH01287250A - Super fine crystal soft magnetic alloy having excellent heat resistance - Google Patents

Abstract

PURPOSE:To drastically improve the heat resistance of the title alloy by suppressing the content of C, P, O, S, N, etc., in a super fine crystal soft magnetic alloy of Fe-Cu-Nb-Si-B system having specific compsn. to specific trace amounts. CONSTITUTION:As the magnetic core material for a high-frequency transformer, choke coil, magnetic coil, etc., a super fine crystal soft magnetic alloy having the compsn. expressed by Formula I and Formula II, in which at least 50% of the structure is constituted of extremely fine grains, having <=1,000Angstrom average grain size measured by the maximum size, having less deterioration of soft magnetic characteristics even if reheated and having excellent heat resistance is manufactured. In Formula I and II, M denotes Co or Ni, M' denotes one kind among Nb, W, Ta, Zr, Hf, Ti and Mo, and in the Formula II, M'' denotes at least one kind among V, Cr, Mn, Al, platinum metals, Zn, Sn, Ge and Ga. As for the quantitative index, 0<=a<=0.1, 0.1<=x<=3, 0<=y<=30, 0<=z<=25, 5<=y+z<=30, 0.1<=alpha<=30, beta<=10 and delta<=0.15 are regulated. delta expressing the amounts of C, P, O, S, N, etc., is extremely trace amounts of <=0.15.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an ultrafine crystalline soft magnetic alloy with excellent heat resistance and used in various magnetic cores such as various transformers, choke coils, and magnetic heads.

[Prior Art] In recent years, amorphous alloys have attracted attention as magnetic core materials for high-frequency lances, choke coils, magnetic heads, etc., and have a high saturation magnetic flux density and excellent high-frequency characteristics, and some of them have been put into practical use. ing.

Amorphous alloys are mainly divided into Fe-based and CO-based.
Although the amorphous alloys have the advantage of having a high saturation magnetic flux density and a lower material cost than the CO-based alloys, they have a higher core loss than the CO-based amorphous alloys at high frequencies for boat fishing, and are less transparent. There is also the problem of low magnetic flux. In addition, Fe-based amorphous alloys have extremely high magnetostriction, and when used as a magnetic core, they have the disadvantage that the magnetic core generates beats and its characteristics deteriorate significantly when impregnated or coated.

On the other hand, CO-based amorphous alloys have small core loss at high frequencies and high magnetic permeability, but have the drawbacks of large changes in core loss and magnetic permeability over time, and insufficient saturation magnetic flux density. Furthermore, since expensive CO is used as the main raw material, a cost disadvantage is inevitable.

Under these circumstances, various proposals have been made regarding Fe-based non-product j6 alloys.

Japanese Patent Publication No. 60-1.7019 states that Fe of 74-84 atomic%, B of 8-24 atomic%, and Si of 16 atomic% or less
and 3 atomic % or less of C, and at least 85% of its structure has the form of an amorphous metal matrix, and the structure is discontinuous throughout the amorphous metal matrix. It has a precipitate of distributed crystalline particles, the crystalline particles have an average particle size of 0.05 to 1 μm and a particle size of 1 to 1 μm.
A magnetic amorphous alloy containing iron and boron is disclosed, which is characterized in that the average interparticle distance is 10 μm, and the particle groups occupy an average volume fraction of 0.01 to 0.3 of the whole. I'm here. The crystalline particles of this alloy are said to be discontinuously distributed α-(Fe, Si) particles that act as pinning points of the domain wall.

Also, in JP-A No. 60-52557, F e, Cub
B c's id (75≦a≦85.0<b≦
0.5.10≦C≦20゜d≦10 and c+d≦30)
A low-loss amorphous magnetic alloy is disclosed. This amorphous alloy crystallizes i'! Heat treated at temperatures below iH degrees and above Gurie temperature.

[Problems to be solved by the invention] Although the core loss of the magnetic core made of the Fe-based magnetomagnetic alloy disclosed in Japanese Patent Publication No. 60-17019 is reduced due to the presence of discontinuous crystal grain groups, the core loss is still large. In particular, there are problems in that magnetostriction is large, which causes beats, and impregnation coating causes core loss and significant deterioration of magnetic permeability, and high characteristics cannot be obtained with cut cores or the like.

On the other hand, the Fe-based amorphous alloy of I-Kaimei No. 60-52557 contains Cu, and the core loss of the magnetic core using it is reduced, but it is similar to the core loss of the magnetic core using the Fe-based magnetic alloy containing crystal grains. Not satisfied. Furthermore, there are problems in that changes in core loss over time and magnetic permeability are not sufficient.

As a result of studies to solve these problems, the present inventors discovered that the Fe-Cu-Nb S'i-B alloy consists of an ultrafine grain structure and exhibits excellent soft magnetic properties. The application was filed under the heading, patent application No. 1986-317+, No. g9, etc.

=4- However, if impurity elements other than the above-mentioned elements are present in these alloys, the soft magnetic properties will deteriorate at relatively low temperatures.

With such an alloy, the heat treatment temperature cannot be raised too high, which imposes manufacturing restrictions, and when reheating is required for bonding, such as in the case of magnetic heads, there are significant manufacturing restrictions.

An object of the present invention is to provide an ultrafine-crystalline soft magnetic alloy with excellent heat resistance.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have discovered that C, P, and O in an ultrafine crystal soft magnetic alloy.

By keeping the S and N elements below a certain level, it is possible to obtain an ultrafine-crystalline soft magnetic alloy with excellent heat resistance, which is particularly capable of high-temperature heat treatment and whose soft magnetic properties show little deterioration even when reheated. Heading: The present invention has been conceived.

That is, the first invention of the present application has the general formula: % formula % (where M is CO and/or Ni, and M' is Nb, W
, Ta, Zr, T (f, Ti and M, at least one element selected from the group consisting of o, Y is C9P, ○, S
, one or more elements of the group consisting of N, a.

X+, YI Zlαl and δ are O≦a≦0.
1゜0.1≦X≦3, 0≦y≦30, 0≦Z≦25.5
≦y + z≦30.0.1≦α≦30, and δ≦O,
1, 5), at least 50% of the structure is fine crystal grains, and the average grain size measured at the largest dimension of the crystal grains is 1000 Å or less. It is an ultrafine-crystalline soft magnetic alloy with excellent properties.

In addition, the invention of Section 2 of the present application is based on the following: General formula: % formula % M "B Y 6 (However, M is Co and/or Nj,
M' is at least one element selected from the group consisting of N)), W, Ta, Zr, Hf, T and MO;
is V, Cr, Mn, A], white metal element, Zn.

at least selected from the group consisting of Sn, Ge, and Ga]
Species element, Y is one or more elements of the group consisting of c, p, ○, S, N, an X+ y+ Z+ α, β and δ
are 0≦a≦0.1, respectively. , 0.1≦X≦3.0.0
≦y≦30, 0≦Z≦25, 5≦y 1z≦30.0.
1≦α≦30. β≦10 and δ≦O, i5), at least 50% of the structure is fine crystal grains, and the average grain size measured at the largest dimension of the crystal grains is 1000 Å or less It is an ultrafine crystalline soft magnetic alloy with excellent heat resistance.

More preferable soft magnetic properties are obtained when the average particle size is 500 Å or less, particularly preferably from 20 to 200 Å.

In the Fe-based magnetomagnetic alloy of the present invention, Fe is 0 to 0.1
Corrosion resistance can be improved by substituting with Co and/or N1 within the range.

However, in order to obtain good magnetic properties (low core loss, low magnetostriction), α'' is limited to 0 to 0.1.

In the present invention, Cu is an essential element, and its content fi
(x is in the range of 0.1 to 3 atomic%. 0, ] J
! If it is less than 3 atomic %, the effect of reducing core loss and increasing magnetic permeability due to the addition of Cu is almost negligible;
If the amount is larger, the core loss may become larger than that without the addition, and the magnetic permeability will also deteriorate. In the present invention, the preferable Cu content X is 0.5 to 2 atomic %, and within this range, the core loss is particularly small and the magnetic permeability is high. Also, C
u has the effect of forming the nucleus of the bccFe solid solution crystal,
It also has the effect of suppressing compound phase formation.

In the present invention, M' has the effect of refining precipitated crystal grains by being added in combination with Cu, and Nb, W
, Ta, Zr, Hf, Ti, and MO. Nb etc. have the effect of raising the crystallization temperature of the alloy by -1-, but due to their interaction with Cu, which has the effect of forming clusters and lowering the crystallization temperature, they suppress the growth of crystal grains and reduce the crystal grains that precipitate. It is thought that the particles will become finer.

The content α of M' is 0.1 to 30 at%, and if it is less than 0.1 at%, the effect of grain refinement is insufficient;
Exceeding atomic % causes a significant decrease in saturation magnetic flux density.

The preferred amount of M' added is 2 to 8 atomic percent.

=8-8j and B are elements particularly useful for refining the alloy composition. The Fe-based magnetomagnetic alloy of the present invention, preferably once Sj
, , B can be obtained by forming an amorphous alloy by adding B and then forming fine crystal grains by heat treatment. Sj
The reason for limiting the contents y and Z of B is that y is 30 at%
Hereinafter, if Z is not 25 atomic % or less and y -1-z is not 5 to 30 atomic %, the saturation magnetic flux density of the alloy will be significantly reduced.

V, Cr + M n r A, ], + platinum metal element I Z n .

At least one selected from the group consisting of Sn, Ge, and Ga
The seed element M'' can be added for the purpose of improving corrosion resistance, improving magnetic properties, or adjusting magnetostriction, but its content is limited to 0 atoms. This is because if the content exceeds 10 atomic %, the saturation magnetic flux density will drop significantly.

C, P, O, S, and N, which are the characteristics of the present invention, are elements that easily enter raw materials as impurities, and when a ferroalloy or the like is used as a raw material, there is a possibility that they are contained in large amounts in the alloy.

As a result of intensive study, these elements were determined to be Fe-Cu-Nb-3.
It has been found that these elements are the cause of the deterioration of the soft magnetic properties during heating of i-B alloys, and the total amount of these elements is 0.15 atomic % or less, and in particular, C: 0.2 atomic % or less, P: 0. 05 atomic % or less, o; o, os atomic % or less.

It has been found that when the S content is 0.02 atomic % or less and the N content is 0.02 atomic % or less, an ultrafine-crystalline soft magnetic alloy with particularly excellent heat resistance can be obtained without the influence of these elements.

These elements tend to form compound phases or segregate, so it is thought that increasing the temperature tends to deteriorate the soft magnetic properties.

[Example] The present invention will be explained below with reference to Examples, but the present invention is not limited to the scope of these Examples.)

Example 1 B with a purity of 99.5% or more, Si with a purity of 99.99% or more
.

Nb with a purity of 99.5% or more, Cu with a purity of 99.9% or more
.

Using Fe with a purity of 99.9% or more, vacuum melting was performed to produce a master alloy. Next, an alloy ribbon having a width of 5 mm and a thickness of 19 μm was produced using this master alloy by a single roll method.

As a result of structural observation using X-ray diffraction and transmission electron microscopy, it was confirmed that this alloy ribbon was an amorphous alloy.

Next, this alloy ribbon was wound with the roll contact surface inside to prepare a toroidal magnetic core, and heat treated in an Ar gas atmosphere. FIG. 1 shows the heat treatment temperature dependence of the magnetic properties of alloy A of the present invention. Note that the heat treatment time was 1 hour.

Next, this alloy A was analyzed. As a result, B; 7.21
at%, S i ; 13.61 at%, N b
; 2.61 at%.

Cu: 1.01 at%, C: 0.022 at%
, P; O,0O1 at%.

0; 0.005 at%, S; O,0O1 at%
, N; 0.001 at%. (Each value is an analytical value of weight%.

This is the value converted to atomic %. ) Comparative Example 1 As a comparative example, the analysis value is B; 7.51 at%, Si
; 13.22 at%, N b ; 2.41 at%,
Cu: 0.99at%.

C; 0.53 at%, P Ho, 8 at%, O;
0.06at%, S; 0.03at%, N; 0
．． Alloy B consisting of 0.3 at% and the remainder substantially Fe was prepared in the same manner as Alloy A, and after being made into a magnetic core, it was subjected to the same heat treatment as Alloy A.

The dependence of the magnetic properties of this comparative alloy B on the heat treatment temperature is also shown in FIG.

In addition, after heat treatment at a temperature of 510° C. or higher, ultrafine crystal grains with a grain size of about 200 grains accounted for most of the composition of both Alloy A and Alloy B.

As can be seen from the figure, in the case of the alloy of the present invention with small amounts of C, P, O, S, and N, heat treatment can be performed at a higher temperature.

Next, the invention alloy A and comparative alloy B, which had been heat treated at 550°C for 1 hour, were heated to 570°C, held for 50 minutes, cooled to room temperature, and the effective magnetic permeability μelk at 1kHz was measured.

As a result of comparing the ratio μa/μ5 of the effective magnetic permeability μelk before and after heating at 1 kHz, the alloy A of the present invention has a value of 0.
97. Comparative alloy B with large amounts of C, P, O, S, and N is 0.0
9, it was confirmed that the present invention has less deterioration of soft magnetic properties due to heating and is superior in heat resistance. Here, μ. is μelk after heating, μ5
is μelk before heating.

Example 2 A wound magnetic core made of an ultrafine crystal soft magnetic alloy having the analytical composition shown in Table 1 was prepared, and heat treated at 570°C in the same manner as in Example 1. The ratio of the values of effective magnetic permeability μelk, μa/μ5, was determined. The results obtained are shown in Table 1.

(Hereinafter, blank space) As can be seen from Table 1, the alloy of the present invention has μ, l/μ of 0
．． It was confirmed that the alloy had an excellent heat resistance of 90 or higher, and there was virtually no problem with deterioration.

On the other hand, comparative alloys that exceed the C9○, P, S, and N ranges specified in the present invention all have μm/μ5 of less than 0.90, and furthermore, beyond this specified range, μa/μ5 suddenly increases.
It was confirmed that the value of μ5 became smaller and the heat resistance decreased.

[Effects of the Invention] According to the present invention, it is possible to obtain an ultrafine-crystalline soft magnetic alloy with excellent heat resistance, so the effects are remarkable.

[Brief explanation of the drawing]

``No.'' The figure shows the dependence of the magnetic properties of the alloy according to the present invention and the comparative alloy on heat treatment temperature. Figure 1 Heat (11 degrees (°C) Procedural amendment (shu) Display of the case 1988 Patent application No. 113966 Name of the invention Related Patent Applicant Address 2-1-2 Marunouchi, Chiyoda-ku, Tokyo Name (5
08) Former Ritsu Metals Co., Ltd. Telephone: Tokyo 284-4642 Contents of the amendment As shown in the attached sheet, Claims (1) General formula: % formula % (However, M is Co and/or Ni, M' is Nb. W, Ta , Zr, Hf, Ti, and Mo; Y is c, p; one or more elements a+ selected from the group consisting of 0, S, and N;
X+ y+Z+ α and δ are each O≦a≦0.1.
, 0.1≦X≦3, 0≦y≦30.0≦2≦25, 5≦
y + Z≦30. An ultrafine-crystalline soft magnetic alloy with excellent heat resistance, characterized by an average of 1000 Å or less. (2) General formula: % formula % (where M is Co and/or Ni, M' is Nb. At least one member selected from the group -1= consisting of W, Ta, Zr, Hf, Ti and Mo) Element, M rr is ■. Cr, Mn, Al, platinum metal element, Zn, Sn. One or more elements selected from the group consisting of Ge, Ga, Y
is at least one element selected from the group consisting of C, P, O, S, and N, an X+ Y+ Z+ α, β, and δ are each 0≦a≦0.1.0.1≦X≦3 .0.
O≦y≦30, 0≦2≦25, 5≦y1z≦30゜0
．． 1≦α≦30. β≦10 and δ≦0.15), at least 50% of the structure is fine crystal grains, and the average grain size measured at the largest dimension of the crystal grains is 1000 Å or less An ultrafine crystalline soft magnetic alloy with excellent heat resistance.

Claims (2)

[Claims] (1) General formula: (Fe_1_-_aM_a)_1_0_0_-_x_-
＿y＿−＿z＿−＿α＿−＿δCu_xSi_yB_z
M'_αY_δ (However, M is Co and/or Ni, M' is Nb, W, T
at least one element selected from the group consisting of a, Zr, Hf, Ti, and Mo; Y is one or more elements a, x, y selected from the group consisting of C, P, O, S, N; , z, α and δ are respectively 0≦a≦0.1, 0.1≦x≦3, 0≦
y≦30, 0≦z≦25, 5≦y+z≦30 and 0.1
≦α≦30), at least 50% of the structure is fine crystal grains, and the average grain size measured at the largest dimension of the crystal grains is 1000 Å or less. Ultrafine crystalline soft magnetic alloy with excellent properties. (2) General formula: (Fe_1_-_aM_a)_1_0_0_-_x_-
＿y＿−＿z＿−＿α＿−＿β＿−＿δCu_xSi_
yB_zM'_αM"_βY_δ (However, M is Co and/or Ni, M' is Nb, W, T
at least one element selected from the group consisting of a, Zr, Hf, Ti and Mo, M'' is V, Cr, Mn, Al,
At least one element selected from the group consisting of platinum metal element, Zn, Sn, Ge, and Ga, Y is C, P, O, S, N
one or more elements selected from the group consisting of a, x, y,
z, α, β, and δ are 0≦a≦0.1, 0.1, respectively
≦x≦3.0, 0≦y≦30, 0≦z≦25, 5≦y+
z≦30, 0.1≦α≦30, β≦10 and δ≦0.1
5), and at least 5 of the tissues have a composition represented by
An ultrafine-crystalline soft magnetic alloy with excellent heat resistance, characterized in that 0% of the crystal grains are fine crystal grains, and the average grain size measured at the maximum dimension of the crystal grains is 1000 Å or less.