JPH04110451A - Amorphous alloy - Google Patents

Abstract

PURPOSE:To improve the toughness of an amorphous Co alloy having superior high magnetic permeability characteristic in a high frequency magnetic field by reducing the content of P as impurity in an amorphous alloy prepared by adding specific proportions of non-metallic elements or further transition metals to a Co-Ni-Fe-Mn alloy. CONSTITUTION:The content of P in the alloy composed essentially of Co and having a composition represented by formula I and formula II, where X+Y=100 atomic % in the formula I and X+Y+Z=100 atomic % and Y<=8 atomic % in the formula II and, further, 13<=Z<=28 atomic % and, by atomic ratio, 0<=a<=0.20, 0<=b<=0.20, and 0<=c<=0.20 in both formulae is limited to <=40ppm. The molten metal of the alloy with the above composition is cooled rapidly by means of chill block melt spinning, by which a ribbon of an alloy with amorphous structure is produced. By this method, the ribbon-shaped amorphous alloy which has uniform quality and superior toughness and in which saturation magnetostriction constant is regulated to a value within the range of + or -5X10<-6> can be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Fields of Application of Blood Industry] The present invention relates to improving the toughness of a Co-based amorphous alloy that exhibits outstanding high magnetic permeability or high angular magnetic properties in a high frequency magnetic field.

(Conventional technology) Conventionally, high permeability technology such as common mode choke coil of switching DX, magnetic l\\rad magnetic sensor, etc.
'lj:' (Wound magnetic cores made of 5ON4-re alloy strips have been used for high square ratio components such as saturable reactors and noise absorbers of Ijj.

Although ferrite has the advantage of low eddy current loss, it suffers from low saturation magnetic flux density and poor temperature characteristics.

Further, although the 5ONi-Fe alloy has a high saturation magnetic flux density and a high squareness ratio in a low frequency range, it has large eddy current loss and hysteresis loss, and cannot be used in high frequency applications.

Therefore, the magnetic flux density is higher than that of ferrite, and 5ON
Amorphous magnetic alloys are seen as promising as high-frequency magnetic alloys, which have lower core loss than crystalline metals such as J-Fe alloys, and have been put to practical use as ten-wound magnetic cores for the two types of applications mentioned above. It became so.

In particular, an amorphous alloy of CO yarn with Go as the main element and a small amount of elements such as Fe, Nj, and M11 whose outermost shell electron number is close to that of CO is saturated and has a strain constant close to zero. Coercive force is small! [S(Magnetic/[Raw 42
It can be said to be the narrowest 4-metal thorn. 13″
(Even in one frequency band, fH: air resistance is high and 15
~ 50 μm (because it is used as a thin ribbon, the eddy current loss is low and it is ferrite).
It has low loss characteristics.

The above-mentioned co-based amorphous alloy with magnetostriction of zero or close to zero is heated and held at a temperature above the Curie temperature, above the Ayu crystallization temperature, and then returned to room temperature at a linear motion speed of 10'C/sec or more. 'Jlj l
It can be used for common mode choke coils, magnetic heads, and various magnetic sensors by increasing its integrity, and it can be used to improve the squareness ratio by imparting -l+1+ anisotropy in the magnetic path direction through magnetic field skewer annealing and cooling treatment. , used in saturable reactors, noise absorbers, etc.
By including a broadly defined transition metal element other than those listed above as a +J additive element, the thermal stability is increased and the saturation magnetostriction constant is finely adjusted. There is. .

[Problem to be solved by the invention]

Conventional magnetic components such as various inductors, sensors, etc.
After producing an amorphous ribbon with a thickness of 15 to 30 ILm by the J1i roll method, it is shaped into a product shape using the following 2]5X method.

One method is to form a wound core by taking an amorphous ribbon of a predetermined width and applying an appropriate gluing force (to increase the core density).
Several kgf/plate l'~several 10 Jf/ml'
) is applied and turned 8 times into an l-roidal shape, and then subjected to optimal heat treatment. One is to stack the ribbon into one magnetic core, and either punch the ribbon with a punching press (mold) or press the ribbon with a die.
・After applying optimal heat treatment to each core unit that has been chemically formed by etching with a strong acid, etc., multiple cores are laminated with an adhesive or the like, and then put together. In both cases, the ribbon used for processing is either manufactured in advance to a predetermined width using molten metal, Q+, or cold +18, or a wide ribbon is cut to a predetermined width using a cemented carbide, high-speed JL/1M, etc. slitter knife. Adjust to the width.

Therefore, in order to commercialize the amorphous ribbon into a product, it is necessary to withstand the tension of the core winding process and to avoid breakage due to bending during the core winding routing. Ribbon breakage inside,
It is required that cracks etc. do not occur 4], and this requires that the molten metal quenched glue has 1', 1'! 1', horn properties, and only 1'! rM,',C,Hbi,11
It is said that it is necessary to do something like that. The presence of angular portions, even locally, is undesirable because it directly leads to cracking and breakage during processing, resulting in halting of processing and a decrease in processing yield.

In the past, ensuring the toughness of amorphous ribbons was achieved primarily through the chemical composition and the ability to form amorphous material from both sides of the ribbon.

In terms of composition, optimization of the types, combinations, and amounts of semimetals such as amorphous-forming elements, and transition metals that contribute to thermal stability and magnetic properties is important. The correlation between the critical cooling rate to become amorphous and the critical maximum thickness to become amorphous was determined. For example, M, Naka, A, 11jo++c and'
Ding, Masu]noto: Sci, 8ep
, Ii do I'UA20(198])+8/], te(
Well, the critical thickness of Co-3i-B3deL alloy is determined experimentally by bonding B) 5i-B half metal, which is said to have the highest formability, and is CO72, + 81.12, 6 B+
It is shown that 5 indicates a maximum of 1 target. Also, )1
．． llagiVllptra, A, InoLlc(+
nd 'll', Masumot, o: Mat
erials Sc, 1encc and Engi
nee Ding, 54 (1982) 1.
97-207. So, (C,': o,
, .

XMX)? ? 1. S ilN, I'3 + hten A, 129 heat wing bow j) The critical thickness ξ when adding up to X = 20 is reported, and in order to increase the critical thickness, I''a,
It is said that it is effective to add up to a certain amount of each element of Nb, V, Mo, and WFe, and that the effects are highest in this order.

In terms of ribbon production conditions, there is nothing that touches on the production parameters of the long-body rabbit roll method, but for example, Ken Masumoto, Kenji Suzuki, Keiyasu Fujimori, Koji Hashimoto: Fundamentals of Amorphous Metals,
Published by Ohmsha (1982) P. 34 contains l')l! specific to each composition. It is necessary to ensure a cooling rate that supersedes the cooling rate in the RL field, and in the same document P. ) and the temperature of the molten material, and the strength of the molten material is determined by the phase forces such as the amount of ejection (depending on the number of nozzle holes and the output pressure of ni'1) and the circumferential speed of the rotating body. is stated.

However, this article only describes the general influence of G element and plate 1 on the ability to form amorphous, and maintains the toughness of the amorphous ribbon, among other things. It is insufficient in terms of uniformity and consistency of quality to improve the level of slander. However, since the composition that can be applied in reality is set from the viewpoint of high frequency magnetism after optimum heat treatment rather than toughness, it is not necessarily the composition that will give the maximum sheet thickness (on the contrary, the composition that will give the maximum sheet thickness or Even if the composition is close to that, it is effective in terms of high frequency magnetism] 5 to 30
There was a problem in that it was not directly linked to the improvement of the brittleness of μIn ribbons.

The purpose of the present invention is to improve the toughness required in various processing steps leading to final products such as cores and sensors of CO-based amorphous alloy ribbons with low magnetostriction, and in particular to improve local brittleness to achieve uniform quality. It is to exclaim.

[Heidan to solve the problem] In view of the purpose of the 112th Book, as a result of intensive investigation, the Kizutomesha:
The so-called magnetostriction is adjusted to zero or near zero, and heat treatment is performed in a magnetic field to achieve a high squareness ratio and low loss! ], obtains unity. Alternatively, in order to obtain high magnetic permeability, Kikory:fl' is heated and kept at a temperature above 10°C and below the crystallization temperature.
In a Co-based amorphous alloy that is put into practical use after being subjected to heat treatment jηI in which it is rapidly cooled at a cooling rate of s e c or higher,
By reducing Mg as an impurity element, the Co
The inventors have discovered that the toughness of molten amorphous alloys is improved in the rapidly cooled state, and have conceived the present invention.

Specifically, the present invention has the following advantages: Sil (wood composition (Co, -0B, Ni, FebMnp
), M7, where M: is the first name or more of an element consisting of B and Sl, x and z are atomic %, and x +7. = 1.00 13≦z≦28 a, b, c are atomic ratios, and the δ:II composition is expressed as 0≦a≦0.20 0≦b≦0.20 0≦C≦0.20 The saturation magnetostriction constant is ±5×1
It is an amorphous alloy within 0' and contains P which is an inevitable impurity (i) 2) is 40 P , P ,
It is an amorphous compound whose 4, S sign is that it is less than or equal to i·I.

In the present invention, the toughness of the amorphous ribbon as stored and quenched is improved by reducing F'. Toughness in this case
i (1 is whether it is the conventional 180° dense foil bending 1M function or the machine)
I haven't detected any bending distortions assuming it's a natural body.] It's a melon.

The toughness rating of 1+lti of the present invention means that the ribbon can be stretched in the width direction at any position in the rihon, &dou direction.
Clutter advance when tearing at speed less than c, 1
This is done by the chief of staff, N.11. In other words, as shown in Figure 1, if the toughness is sufficient, the fracture line will be zigzag in the micro-lung 1, etc., depending on the propagation of the crack or the bow tearing speed, but from a macroscopic perspective it will be straight. move on. In the brittle case shown in FIG. 2, the crack propagates faster than the tearing speed, and the fracture line is straight, but macroscopically the direction is warped, and the -+1jli ribbon is chipped. It may occur. A similar classification can be made by observing the fracture in a normal bow tension test, for example, by observing the fracture in a normal bow tension test. The second thing is that there is a possibility that numbers are poets, and in actual inspection, the tearing method described in 1. Even if the ribbon size is m'+, so-called ζ) 180" close bending may be possible, and the brittle part is limited to a part of the ribbon instead of the entire length in the width direction, as shown in Figure 3. In some cases,

The present inventors have newly discovered that by reducing the P content, the frequency of occurrence of cystic areas is reduced.

If there are non-metallic inclusions in the tearing part, the ribbon will become brittle, so gas components in the molten metal passing through the nozzle,
The content of AI, S, etc. is sufficiently low, for example 0. (50
ppm, N2<25ppm, A1<40ppm, S
<30 ppm), and - JI inclusion area ratio in the master alloy
It is preferable that the concentration is 0.012% or less when recorded by the S method, and that the long ribbon is not so bent that non-metallic inclusions appear at various locations.

The mechanism by which ribbon toughness is improved by reducing P is not clear, but by analyzing the impurities in the amorphous ribbon, we can detect the P content and verify this result by comparing it with the tear test results mentioned above. Chill.

The amorphous alloy of the present invention having the above composition with a low content of P (11)- can be prepared by rapid t1) from molten metal;
"It can be manufactured according to □11.Industrially,
A method in which an alloy is melted in a high-frequency furnace or an electric furnace, and the molten alloy is ejected from the tip hole (round or rectangular) of a crucible using gas pressure, and is solidified by contact with the surface of a rotating cooling body to form a ribbon. applies. Generally, a method called the single roll method, that is, a method in which the outer surface of a roll is used as a rotating body for cooling, is common.

Normally, a master alloy is melted in advance, and this master alloy is -[
Since P is often remelted in the crucible, it is necessary to reduce the amount of P during melting of the master alloy. There are various methods for this purpose, but impurities can be reduced by carefully examining the purity of the raw materials, various conditions including temperature control during melting, sludge removal, and construction, and sand prevention in the case of spinning molds, especially sand molds.

The reasons for limiting the composition, which is the basis for reducing the amount of P, will be described below.

As mentioned above, the low JJt loss at high frequencies requires that the distortion be zero or close to zero, specifically, saturation within ±5X]O'* # constant For that purpose, Co, N i ,
If the atomic ratio of F e Mn is adjusted appropriately,
In (Col-3, Ni, FebMr+c), a
, b, and c can each be implemented in a combination within the range of 0 to 0.20. When any one or more of a, b, and c exceeds 0.20, the saturation magnetostriction constant exceeds +5×10−.

Bright - The metal element M is one or more of B, Si, and 13
The content must be at least 28 atomic %.

If it is less than 13 at%, amorphous formation becomes difficult,
If it exceeds 28 atomic %, it becomes difficult to form an amorphous layer and the saturation magnetization decreases significantly. B.

S] is 15 Normal single roll method rocking speed IQ″~]0°
In 'C/Sec, it is only B that can form an amorphous state in Jp alone, and Si is 13 with a content of 5 at% or more.
Which compound addition is required?

In the present invention, (Co, , b INi, Fe
) Mn6) -j'll as the transition element '↓゛1
．． 3△, 4/\, 5△6 no° 7/\, excluding Mll
1 ゛ (high CO, ?\'l except < 8 he 5 original wo) (place 1 1 X. These are l Fi'.

It can be contained up to a total of 8 atomic percent or less, but 8
If it exceeds atomic %, the saturation magnetization will significantly decrease or amorphous formation will be difficult.

〔Example〕

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [Details 1] of the present invention will be explained by way of examples.

Examples] In atomic %, (COl, !14Fel, oj12Mo
n S III Bo.

An amorphous alloy ribbon was manufactured. .

Prior to manufacturing the ribbon, the master alloy was melted. Dissolution is Co, B
After selecting two types of raw materials each, the composition was changed, and the content of impurities was changed using a total of six types of raw materials. Other Fe,
M○ remained constant. Melt at 1450°C, 1350°C
The molten slag generated at °C was removed and cast into a cast iron mold at 1280 °C.

2.5 kg of the Nijiku alloy was remelted in a quartz crucible and molten at 1280'C.
ulm J ugly rectangular slit, 30
Rapidly solidify with Onunφ's chromium copper single roll-]-,
5 o] m width x] 9 to 25 μn 1 thickness and length approximately 3000
It was made into an amorphous alloy ribbon of m. .

Spread this alloy ribbon over ``k'':'+O□ t
o It was torn into pieces and the toughness was evaluated. Tearing was performed 20 times at each position in the longitudinal direction, and if there was a deviation of 2 nnn or more from the tear direction, it was assumed that a brittle part existed, and the brittle fracture 111 rate (%) was calculated for each position. compared.

Table 1 shows the P content of amorphous alloys made of five types of master alloys and the brittle rupture rates of these amorphous ribbons.

The lower the P content, the lower the brittle failure rate at 1δ.

These five types of ribbons have an outer diameter of 22 m1Ilφ and an inner diameter of 14
The number of stops due to adhesive bond breakage during winding when the film was wound into a toroidal shape of 1IIIφ and 5 mm thick was determined. In this case, the tension applied to the ribbon is approximately 12
kgf/nun 2, the ribbon has 10 songs in the device
The direction of travel is changed 180° three times using the RO guide reel. This J, eel-wound magnetic core manufacturing equipment is not particularly designed, and the load applied to the ribbon varies depending on the mounting and product specifications, but this example is given as a guideline. It is.

The length of each ribbon], the number of breaks per 000 m ↓) is 2, 15.2/N, I-N O, 5, respectively.
1, 95,120 times.

If the above value is less than 40P, P, and M, the toughness of the as-quenched polymer will be improved, and especially the local brittleness will be reduced, and the effect will be large.1 Example 2 Atomic %, (CO+, += Feo, ciLi S 1
Example 1 using an amorphous alloy ribbon of 15 Bs
Using the same method as above, I created 51 x 1 of χ (same as the ribbon of 1).

Furthermore, 816 types of alloys were obtained by selecting two each of Co and B 31 types and changing their composition.

Table 2 shows that the amorphous alloy ribbons made of five types of -IU alloys show no breakage rate.

As the content of P decreases, the number of 11/ij fractures at each position decreases, and if the deviation exceeds 60], P, and M, local embrittlement will be greatly improved. I know it will happen.

Fire Example 3 At %, (Co,,,,!”e.,.,Mu., o
+ L s N I) + ``Using an amorphous alloy ribbon of VVS116BB, a ribbon was produced and evaluated using the same method as in [1].

! J alloy was made into two types by changing ■3 original slope. 2 in Table 3
The P@ content and the lll'iv rupture rate of the amorphous alloy ribbon according to the seed mother alloy are shown.

In the example of the present invention where the content of L' is low, Ill'
i+・B1. Gu I 1 rate or a・Mr. little, II/lχ・
[1] You can see that it can be changed by changing i, l, or breaking. .

Example 4 In atomic %, (Go.=!l :+ F eo, O'
2 M II. ,. ,),. Cr.

Using an amorphous alloy ribbon of Si1°B8, a ribbon was manufactured in the same manner as in Example 1 and evaluated.

The mother alloy was changed from B Koboku to two types. Table 4 shows the P content of amorphous alloy ribbons made from two types of alloys.
Indicates the brittleness failure rate.

It can be seen that in the examples of the present invention where the P content is low, the brittle class]υ1 ratio is lowered and the brittle force is improved.

Example 5 In atomic %, (CO8+ir←,,.2Fe.oh)+b
N1. ), T a, Ru, S i,. Using the amorphous alloy ribbon B3, ribbons J and Ri'W were manufactured and evaluated in the same manner as in Example.

The U alloy is B river (2+ weight was changed by changing the weight.Table 1 shows the P content and the wave breakage ratio of the amorphous alloy ribbons made of two types of FFJ alloys.

In 111 cases of wood with low P content i6 (: 1 brittle fracture chamber or aφ; it was found that the brittleness was changed slightly; 1; ζ)
.

1:1 [Effects of the Invention] The amorphous alloy of the present invention improves the toughness of various cores for high frequencies, sensors, etc., which are necessary in each processing process leading to the final product, and improves production yield and efficiency. It has a high industrial value.

[Brief explanation of drawings]

Fig. 1 is a schematic diagram showing a tear state of a ribbon without local IJQ properties, which is the target of the present invention; Fig. 2 is a schematic diagram showing a brittle tear state; FIG. 2 is a schematic diagram showing a state in which the

Claims (1)

[Claims] 1 Basic composition (Co_1_-_a_-_b_-_cNi
_aFe_bMn_c)_XM_Zhere, M:B,S
one or more elements consisting of i, x and z are atomic %, x+z=100, 13≦z≦28 a, b, c are atomic ratios, 0≦a≦0.20, 0≦ b≦0.20 0≦c≦0.20 The saturation magnetostriction constant is ±5×10^-
It is an amorphous alloy whose P content (weight), which is an inevitable impurity, is within 40P. P. An amorphous alloy characterized by having a molecular weight of M or less. 2 Basic composition (Co_1_-_a_-_b_-_cNi
_aFe_bMn_c)_XT_YM_Zhere, T:
One or more elements consisting of transition metal, M:B, Si, x
, y, z are atomic %, x+y+z=100, y≦8, 13≦z≦28 a, b, c are atomic ratios, 0≦a≦0.20, 0≦b≦0. 20 0≦c≦0.20 The saturation magnetostriction constant is ±5×10^-
It is an amorphous alloy whose P content (weight), which is an inevitable impurity, is within 40P. P. An amorphous alloy characterized by having a molecular weight of M or less.