JPS58144448A - amorphous magnetic alloy - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention essentially consists of the constituent elements of the alloy composition.

Made of C0-Mo-Zr system, with high corrosion resistance and high wear resistance;
The present invention relates to an amorphous magnetic alloy that has high thermal stability, low magnetostriction, a saturation f0 flux density of 7 kG or more, and excellent soft magnetic properties, and a heat treatment method for the same.

Utilizing the excellent soft magnetic properties of amorphous magnetic alloys, attempts have been made to apply alloy systems with nearly zero magnetostriction to magnetic heads or magnetic cores for cartridges and the like. However, C
o -Fe -Si -B amorphous magnetic alloys generally have poorer wear resistance than sendust.

In addition, alloy systems that improve this have the disadvantage that the saturation magnetic flux 10 density is less than 8 kG, and in terms of thermal stability, the initial magnetic permeability changes greatly over time.

There are problems such as digitization.

On the other hand, a metal-metal amorphous magnetic alloy essentially containing Zr as the vitrifying element has a high crystallization temperature and exhibits high thermal stability. But this.

Even these alloys have both corrosion resistance and wear resistance.

It was difficult to obtain an alloy system with high saturation magnetic flux density and high magnetic permeability.

In view of the above points, the present invention has superior corrosion resistance and wear resistance 20 than Sendust, has a high crystallization temperature, has excellent thermal stability, has extremely low magnetostriction, and has a relatively high saturation magnetic flux density. It is also softened by heat treatment.

We propose an amorphous magnetic alloy that can significantly improve magnetic properties.

The purpose is to provide

The present invention achieves the above objects by the following inventions (1) to (3).

It was designed to achieve the following.

(1) The compositional formula is CoaMol, Zr, BdMe, and M is Mn, Fe, Ni, Cr, Nb, T
i, from the group consisting of Ru.

at least one metal element selected from 1″a
, b, c, d, and e each indicate the percentage of atoms, and 79≦a≦86, 2≦b≦12, 7≦C≦1
1゜0≦d≦3, 0≦e≦5, a+b+c+d+e
= 100, is predominantly amorphous, has an extremely small magnetostriction of -IXIO-6 to +IX10-6,
High saturation magnetic flux density of 7 to 13 kG, corrosion resistance,
Amorphous magnetic alloy with wear resistance higher than Sendust.

(2) The composition formula is represented by qo;, f, MobZroB, Me, and M is ・Mn, Fe, Ni, Or, Nb,
A small number selected from the group consisting of Ti and Ru (
Both are one type of metallic element, and a, b, c, d, and e each indicate the percentage of the number of atoms, and 82≦a≦86, 2≦b≦7, 7≦C≦ 9
゜0≦d≦3.0≦e≦5, a+b+c+d+e =
The strength of rotating an amorphous magnetic alloy satisfying 100 at a speed of 5 revolutions per second or more substantially reciprocally with the alloy sample
In a magnetic field of kG (kilo Gauss) or higher, the heating/cooling rate is 1°C or more per minute, and the temperature range is 200°C or higher and 5°C or lower than the crystallization temperature of the alloy for 1 minute.

It is heat treated for 1 hour, has an extremely small magnetostriction of -IX 10-6 to +I

An amorphous magnetic alloy with a magnetic field higher than that of Sendust and excellent soft magnetic properties.

(3) The compositional formula is CoaMo5Zr, BdM, , where M is.

Mn, Fe, Ni, Cr, Nb, Ti, R
A small number selected from the group consisting of u (all are one type of metal element, and a, b, c, d, and e each represent a percentage of the number of atoms.

79≦a≦81, 7≦b≦12. 10≦C≦1
1. .

0≦d≦3. 0.01≦e≦5, a+b-1-c-
An amorphous magnetic alloy that satisfies 1-d+e = 100 is heated and cooled at a rate of 100°C or higher for 1 time, and the temperature is 5°C higher than the crystallization temperature of the alloy.
for 1 to 10 minutes at a temperature range of 100°C lower.

After heat treatment, the magnetostriction is -I x 10-6 to +I x
10-6 and the ultimate.

An amorphous magnetic alloy with a crystallization temperature of 550°C or higher, corrosion resistance and wear resistance higher than Sendust, and excellent soft magnetic properties.

In the present invention, the magnetostriction of the Co-Zr amorphous alloy is small.

In particular, the alloy system containing MO as shown in the first aspect of the invention is easy to amorphize and is excellent.

Among this alloy system, it was found that the alloy exhibited excellent thermal stability, high corrosion resistance, and high wear resistance.

In the alloy having the composition range shown in the second invention, as shown therein.

By applying heat treatment as described above, the alloy having the composition range shown in the third aspect of the invention can be produced.

By applying such heat treatment, the soft 1) magnetic properties of these alloys are significantly improved, resulting in high magnetic permeability suitable for practical use.

It was completed by successfully obtaining the following.

The alloy composition of the present invention is essentially Co, Mo, Zr
The three elements.

By adding a small amount of B element as necessary, the soft magnetic properties can be improved and it can be easily made amorphous.

In addition, the magnetostriction is further adjusted to zero using additive elements, while improving wear resistance and corrosion resistance, resulting in high saturation.

Measure magnetic flux density and high crystallization temperature (high thermal stability).

It is something that

Here, in order to increase the saturation magnetic flux density to 10 kG or more, Co
It is necessary to make the amount of Co more than 82 atomic %.

When exceeding 8696, Zr must be 7 hara to make the magnetostriction zero.

%, making it difficult to make it amorphous. Because of that,
It is desirable that the amount of Co be 86 atomic % or less.

In addition, in order to make the saturation magnetic flux density 1 okG or more, magnetic 10
The amount of MO to adjust the strain to zero needs to be at least 2 atomic % or more and 7 atomic % or less. Zr as a vitrification element
The amount needs to be at least 7 atomic % as an amount that can easily become amorphous, and if this amount exceeds 9 atomic %, CO
The amount of magnetic elements such as
Since it is less than kG, it is necessary to suppress it to less than 9 atomic percent. Addition of a small amount of B element promotes amorphization, but
If it exceeds 4 atomic %, the ζ initial magnetic permeability decreases rapidly, resulting in deterioration of soft magnetic properties and a decrease in saturation magnetic flux density, so the B X2'1 element needs to be 3 atomic % or less. . In addition, by adding a small amount of metal elements, magnetostriction,
Optimize the saturation magnetic flux density, crystallization temperature, and Curie temperature.

In particular, corrosion resistance is achieved by adding small amounts of Cr, Nb, Ti, Ru, etc.

However, if it exceeds 5 atomic %, the saturation magnetic flux density decreases significantly.

Therefore, it is preferable to make it less than that. this.

A composition having the composition shown in the second invention obtained in this way.

Since the Curie temperature of gold thread is higher than the crystallization temperature, the soft magnetic properties cannot be improved by the conventional heat treatment method of rapidly cooling gold thread from a temperature above the Curie temperature and 10 degrees below the crystallization temperature in a double-stranded magnetic field. Heat treatment is performed in step 2.

(This is because crystallization occurs and the magnetic properties deteriorate). .

However, a rotating magnetic field as shown in the second invention.

Due to heat treatment inside, the initial magnetic permeability is more than 10 times higher1)
succeeded in improving the In improving the soft magnetic properties of an amorphous magnetic alloy by pretreatment in a rotating magnetic field as shown in the second invention, if the rotation speed of the magnetic field rotating relative to the sample during heat treatment is too slow. On the contrary, the magnetic anisotropy will become stronger and the feel of the rock will deteriorate, so it is desirable to rotate at a speed of at least 5 revolutions per second. Also, apply.

When the strength of the external magnetic field becomes less than 1 kG, the magnetic field inside the sample.

The strength of the external magnetic field 5 needs to be 1 kG or more to reduce the effect of constantly rotating the magnetization of the magnetic field 5 and induce magnetic anisotropy. Heat treatment temperature.

The temperature is above the temperature at which atoms can diffuse, and crystallization occurs.

No temperature is desirable. However, the temperature is too low.

Heat treatment takes a long time and increases costs, so a relatively short heat treatment is effective.Heat treatment is performed in a temperature range of 200℃ or higher and 5℃ lower than the 13ζ crystallization temperature for 1 minute or more and 1 hour or less. do. By this heat treatment, in particular, the initial magnetic permeability, l'i (l kHz), was reduced to 1oooo
It is possible to obtain high magnetic permeability of . The faster the sample heating rate is, the more desirable it is, but the cooling rate should be set so that the temperature at which the sample is taken out is below 100°C (5 to 30°C).
/min). This means that high temperatures
When the sample is taken out of the heat treatment furnace and cooled, stabilization of magnetization occurs during the cooling period, resulting in changes in magnetic anisotropy, hardness,
This is because the soft magnetic properties deteriorate. 20. 8. On the other hand, the alloy composition shown in the third invention is characterized in that a particularly high crystallization temperature (high thermal stability) of 550°C or higher is obtained by reducing the Co content to 81 atomic % or less. It is said that However, if the amount of Co is too small, the saturation magnetic flux density will become small, so in order to obtain a high saturation magnetic flux density suitable for practical use, it is necessary to make the amount of Co 79° at % or more. This range of Co amount.

In this case, the amount of MO is set to 9 atomic % or more and 12 atomic % or less.

This allows the magnetostriction to be adjusted to zero. child.

In the case of
Needs to be +1. The amount of B is as described in the second invention.
For the same reason as stated above, it is desirable to keep the content to 3 atomic % or less. By adding a small amount of metal elements to this alloy system characterized by its high crystallization temperature,
Magnetostriction and saturation magnetic flux density are optimized, especially Or, Nb,
It has become clear that adding small amounts of Ti, Ru, etc. can significantly improve corrosion resistance6 and wear resistance.

Ta. This high bond has added high corrosion resistance and high wear resistance.

Alloy systems with a crystallization temperature have a Curie temperature, Tc.

Crystallization temperature, slightly higher or lower than Tx2
The soft magnetic properties of this alloy system can be further improved significantly by heat treatment for a short time of 1 minute or more and 10 minutes or less as shown in the third invention. In addition, in this heat treatment method, the heat treatment temperature is

It is desirable to select a temperature range 5 that is close to the crystallization temperature and lower than the crystallization temperature. Also, the cooling rate after heat treatment.

It is desirable that the cooling rate be faster than that of water cooling. The amorphous material according to the third invention thus obtained.

Highly magnetic alloys are initially used in high frequency bands of 500 kHz or higher.

The magnetic permeability is particularly high at over 400 (and the crystallization temperature II
Since I is also high, over 500°C, the video head's magnetic co-
Suitable for wood. On the other hand, the amorphous magnetic alloy obtained by the second invention has a saturation magnetic flux density higher than that of Senderst, and has a high initial magnetic permeability of 10,000 or more in the low frequency range. ) Suitable for the magnetic core material of heads. As above.

The amorphous material according to the second and third inventions obtained by.

The initial magnetic permeability of the magnetic alloy is 85°C after heat treatment for 2 hours.

There was almost no change, indicating high thermal stability. .

The amorphous magnetic alloy O having the alloy composition of the present invention can be manufactured by any of the ultra-quenching methods such as a single roll method, a twin roll method, and a sputtering method. Crystalline ribbon thin.

An amorphous thin film formed by a band or sputtering.

It can be made with. Further, the magnetic core obtained according to the present invention can be used in magnetic heads, audio cartridges, etc.

It can be used for.

The present invention will be explained below with reference to Examples.

Example 1 Various alloys 0 having the composition range shown in the third invention are melted, and the molten metal is heated in the air or in a vacuum (10-1 mmH).
g or less), from a rectangular nozzle with a diameter of 0.3 x 6 mm or a circular nozzle with a diameter of Q and 4 mm, at a pressure of 0.1 to 3 kg/cm2 and a surface velocity of 50 to 1 second.・Diameter 400 rotated to 80m
Using the single roll method to feed on the surface of a 13 mm iron or copper roll, the width is 1 to 5 mm and the thickness is 11 to 20 mm.
A μm ribbon-shaped amorphous magnetic alloy was fabricated.

To measure magnetic permeability, a ribbon cut to a length of 20 cm was wound into a toroidal shape with an inner diameter of 4.2 mm, and
・ 11. Measured at a dynamic magnetic field of 1 moe or less. The obtained permeability thus represents the true initial permeability, μ. Coercive force, saturated.

The above toroidal sample was also used to measure the sum magnetic flux density.

Insulated copper wire was wound 20 x 60 times (measurements were made by winding the insulated copper wire 20 x 60 times.To measure the soft magnetic properties, a DC magnetization curve measuring device was used to measure the soft magnetic characteristics.
Using.

Figure 1 shows a typical example of the above alloy systems.

FIG. 2 is a diagram showing the relationship between heat treatment temperature, Ta, and initial magnetic permeability, μ, in CoBI Mo7Zr1 (IRu2 amorphous alloy).

In the same figure, curves 1 and 2 are 1 at each temperature and Ta.
0 Initial permeability at 20 kHz measured at room temperature for water-cooled samples after annealing for 1 and 5 minutes, respectively,
The change in μL is shown. In addition, the arrows indicated by Tc and Tx in the same figure
The marks indicate the Curie temperature and the crystallization temperature, respectively, and the ◎ marks indicate the magnetic permeability of the as-prepared sample before heat treatment. As is clear from the figure, Tc and Tx.

Magnetic permeability is significantly higher in an extremely narrow temperature range with low temperature.

You can see that it is rising. In particular, maximum values can be obtained.

When the annealing time is increased at 550°C, the result is 10 minutes or more.

Then, μi (20kH2) deteriorates to about 150, so
Annealing 〇・ 12・ The time is preferably 10 minutes or less and 1 minute or more.

Pre-treat for 5 min at a temperature lower than such Tc, Tx.

The magnetic properties of the above-mentioned amorphous alloy are crystallized by water cooling after processing.

It is shown in Fig. 2 together with the temperature at which the temperature changes and the Curie temperature. In the same figure, CA in the heat treatment condition column indicates that the above heat treatment was performed five times, and the temperature value indicates the heat treatment temperature.

From the same figure, these amorphous magnetic alloys have a saturation magnetic flux zone.

The temperature is 7kG or higher, and the crystallization temperature is 560℃ or higher.

It exhibits high thermal stability and high magnetic permeability.

Therefore, it is suitable for audio and video head materials.

Example 2゜ Amorphous magnetism having the composition shown in the second invention.

The alloy (width 5 mm, thickness 12-17 μm) was rolled using a single roll method.

It was prepared under the conditions described in Example 1 in a vacuum of 10 −2 mmHg or less. Fabricated amorphous alloy ribbon.

A disk with a diameter of 5 mm was cut out from this disk sample.

In a DC magnetic field, the magnetic field direction and disk surface are parallel to each other.

The specimen was placed in a holder and heat-treated at a predetermined temperature while being rotated.

(This heat treatment is abbreviated as rotating magnetic field heat treatment or RFA.

). After heat treatment, a ring with an inner diameter of 3 mm and an outer diameter of 5 mm was punched out from the disk, and the magnetic permeability, coercive force, etc. were measured.

Feeling was measured. In this case, heat treatment in a rotating magnetic field.

sample rotation speed, heating/cooling rate, and annealing.

The time is 720 rpm, 20℃/min, respectively.
It was constant at 20 minutes. In addition, the magnetostriction of this alloy system is all 1x106 or less.

The alloy composition is determined so that

The main magnetism of the representative amorphous magnetic alloy within the composition range of the third invention subjected to the RFA heat treatment as described above.

The characteristics are shown in Figure 2 along with the crystallization temperature and Curie temperature. In the heat treatment condition column of the figure, heat treatment temperature, external field, and magnetic field are shown in that order.

Figure 3 shows CoB2.3 Mo 6g ZrB5B2 M
n0.5 and CoB2,3 Mo6,4 ZrB,3 B
2) The initial magnetic permeability of the amorphous magnetic alloy (after heat treatment in a rotating magnetic field of the as-prepared sample without heat treatment) is a function of the strength of the external magnetic field during heat treatment.

It is shown closed. From the same figure, the external magnetic field is 1°ko
The initial permeability of the sample is as it was prepared when it is greater than e.

It is thicker (rises) compared to (external magnetic field, na=o).

I understand. In addition, the heat treatment temperature is over 200℃, making it scarlet.

Magnetic permeability of the alloy having the composition of the second invention by heat treatment in a rotating magnetic field at a temperature range 10° C. lower than the crystallization temperature.

(It turns out that it can be improved. Magnetostriction.

Even if it is amorphous, for example, CoB5 Cr6 Zrg.

Although the soft magnetic properties of magnetic alloys can only be slightly improved by heat treatment in a rotating magnetic field (the magnetic permeability at 20 kHz is .

1000 or less), especially the alloy composition shown in the third invention.

By this heat treatment method in a rotating magnetic field, the soft magnetic properties can be significantly improved.

Example 3.10 Using the alloy sample shown in FIG.
As a result of measuring the amount of wear, the amount of wear when the test time was 20 hours was 1
All samples showed good abrasion resistance. Furthermore, even in a 100 hour salt water/spray test, the material shown in Figure 2 showed better corrosion resistance than Sendust.

Example 4゜C080,5MO? , 6 Zr10CrIRu4 amorphous magnetic alloy pre-treated Hayashi 0.15. Gear length ~ 0.4 μm 1 core thickness 140 μm
, drawing processing to a track width of 20 μm (using glass bonding).

We prototyped a head with high coercivity and evaluated its video head characteristics.It was combined with a high-coercive metal tape.

When compared to the conventional Mn-Zn ferrite head
For combination with 5CO-γ-Fe203 magnetic powder tape.

At 1 to 6 MH2, the C/N improved by about 6 dB or more and by 2' dB or more.

Ta.

As is clear from the detailed description above, the present invention essentially consists of an amorphous () consisting of a ternary system of Co-Mo-Zr.
High quality magnetic alloys have high crystallization temperatures and high thermal stability.

・In the magnetic core using this amorphous magnetic alloy, ・The magnetic head in particular shows excellent wear resistance, and is superior to high-coercivity camera and tar tape. It was found that 1) high output and C/N improvement can be obtained.

[Brief explanation of drawings]

Figure 1 shows CQ8] MO7Zrl6Ru2 Various amorphous magnetic alloys. Initial permeability at 20 kHz of samples obtained by water cooling after annealing for 1 min (curve 1) and 5 min (curve 2) at a temperature of 21
1.16 ・Line showing the change in μ2 as a function of annealing temperature and Ta
, FIG. 2 shows the main characteristics of the amorphous magnetic alloy of the present invention after annealing. A diagram showing the magnetic properties, Figure 3 is CoB23Mo6g Zr
B, 3 B2 Mn0.5' and CoB2,3Mo6,
4ZrB3B2NilZrB5B2Nil in changing magnetic field. Line showing the initial permeability, μ, at 20 kHz after heat treatment at 350° C. for 20 minutes as a function of the external magnetic field, Ha. It is a diagram. 11 Representative Patent Attorney Junnosuke Nakamura1)

Claims (1)

[Claims] 1. The compositional formula is Co2Mo1. ZrcB, IMete is shown, Mka5Mn, Fe, Ni, Or, Nb, T
At least one metal element selected from the group consisting of i, Ru, Rh, and Cu. So, a, b, c, d, and e are each a percentage of the number of atoms. 79≦a≦86, 2≦b≦12.7≦C≦
11. O≦d≦3.0≦e≦5, a+b+c+d+e
A non-quality magnetic alloy characterized by satisfying 1f+=100 and being predominantly amorphous. 2. The composition formula is shown as CoaMo, zroBdMe, and M
・Mn, Fe, Ni, Cr, Nb, Ti,
At least one metal element selected from the group consisting of Ru, Rh, Cu, a, b,
c, d, and e each indicate the percentage of the number of atoms, and 82≦a≦86.2≦b≦7, 7≦C≦9.・0≦
d≦3, 0≦e≦5, a+b+c+d-1-e =
An amorphous alloy that satisfies 100 is heated and cooled in a magnetic field with a strength of 1 kg 2 Gauss or more that rotates at a speed of 5 rotations per second or more relative to the alloy sample, and the heating and cooling rates are Claims characterized in that the alloy is heat-treated at a temperature of 5° C. or higher for 1 minute at a temperature of 200° C. or higher and 5° C. or lower than the crystallization temperature of the alloy for 1 minute to 1 hour. The amorphous magnetic alloy described in item 1 below. 3 The compositional formula is shown as 00303M0bzrcBd, and M
but. Mn, Fe, Ni, Cr, Nb, Ti, R
Of the group consisting of u? At least one metal element selected from the following. a, b, c, d, and e each indicate the percentage of atoms. 79≦a≦81, 7≦b≦121 10s; C≦1
1. ``'0≦d≦3.0.01≦e≦5,
An amorphous magnetic alloy that satisfies a-1-b+c+d+e = 100 is heated and cooled at a rate of 10°C or more per minute.
- than the crystallization temperature of the alloy. 1 to 10 minutes at a temperature range of 5°C to 100°C lower. 1. The amorphous magnetic alloy according to claim 1, wherein the amorphous magnetic alloy is heat-treated.