JPS6017019B2 - Iron-based boron-containing magnetic amorphous alloy and its manufacturing method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to iron-shelf-based amorphous metal alloy compositions, and more particularly to amorphous alloys containing iron, shelf elements, silicon, and carbon and having enhanced high-frequency magnetism. Various studies have demonstrated that it is possible to obtain solid amorphous materials from certain metal alloy compositions. Amorphous materials have long range atomic regularity (lo range
It is characterized by an X-ray diffraction cross section (Prome) consisting of a broad intensity maximum. Such a cross section is qualitatively similar to the diffraction cross section of a liquid or a normal window glass. This is in contrast to crystalline materials, which produce diffraction cross sections consisting of sharp, narrow intensity maxima. These amorphous substances exist in a metastable state. When heated to a sufficiently high temperature, they give off a heat of crystallization and crystallize, and the X-ray diffraction cross-section changes from having amorphous characteristics to having crystalline characteristics. U.S. Patent No. 3,856,513, issued December 24, 1974; S. Chem and D. E. Because of PolW,
A novel amorphous metal alloy is disclosed. These amorphous alloys have a composition represented by the formula NLYbZc. Here, M is at least one metal selected from the group consisting of iron, nickel, cobalt, chromium, and vanadium, and Y is at least one element selected from the group consisting of phosphorus, shelf elements, and carbon, Z is at least one element selected from the group consisting of aluminum, antimony, beryllium, germanium, indium, tin, and silicon, and "a" is about 60 to 90 atomic percent, and "b" is about 10 to 30 atom%, “
c'' is about 0.1 to 15 atomic percent. These amorphous alloys have been found to be useful in a wide variety of applications in the form of ribbons, sheets, wires, powders, etc. The Chem and Polk patent further states that the formula Ti
An amorphous alloy having Xi is disclosed. Here, T is at least one transition metal, X is aluminum,
antimony, beryllium, shelf elements, germanium, carbon,
At least one element selected from the group consisting of indium, phosphorus, silicon, and tin, and "i" is about 70 to 87
atomic %, where "i" is approximately 13 to 30 atomic %.
These amorphous alloys have been found to be suitable for wire applications. At the time the amorphous alloys mentioned above were discovered, they were shown to have superior magnetic properties than the polycrystalline alloys known at the time. Nevertheless, efforts have been needed to develop additional alloy compositions for new applications with improved magnetic properties and higher thermal stability. The present invention provides an iron-based columnar magnetic alloy having at least 85% of its structure in the form of an amorphous metal matrix. The alloy has been annealed at a temperature and for a sufficient time to induce precipitation of discretely distributed crystalline particles of its constituents. The discontinuously distributed crystalline particles precipitated by the alloy have an average grain size ranging from about 0.05 mm to 1 mm, and about 1 mm to 10 mm.
It has an average interparticle distance of about 0.01 to 0.0.
The average volume fraction (volmmeFr
action). Dawn hammering of alloys is carried out in the presence of a magnetic field. However, it has been found that by dulling the alloy in the absence of a magnetic field, very good magnetic properties can be obtained at reduced manufacturing costs. Preferably, the alloy consists of a composition having the formula PeaBbSicCd, where "a", "b", "c", and "d" are
about 74 to 10, 8 to 24, 0 to 10 and 0 to 3, atomic %, respectively, and "a", "b", "c"
, and "d" is 100. Furthermore, the present invention also provides a method for increasing the magnetism of the above-mentioned alloy, which method consists of the following steps {a', {b}, 'c}. that is, {a} forming the alloy into a continuous ribbon by nching a melt of the alloy at a rate of about 1 to 1 pC/sec;

[b} applying an insulating layer such as magnesium oxide to said ribbon; Anneal at a sufficient temperature and for a sufficient period of time. The alloy produced according to the method of the present invention can be observed by x-ray diffraction,
The result is less than 30% crystalline, more preferably less than about 15% crystalline, as determined by electron diffraction or transmission electron microscopy. Alloys produced by the method of the present invention exhibit improved high frequency magnetism that remains stable at temperatures up to about 150°C. As a result, the wire alloys are suitable for applications such as energy storage inductors, pulse transformers, transformers for switched-mode power integration, current transformers, and the like. The present invention will be better understood, and other advantages will become apparent, from a consideration of the accompanying drawings. Figure 1 shows the induction (iM ratio) for an amorphous alloy in which there are no precipitated crystalline particles with a discontinuous distribution.
It is a graph showing the relationship between and magnetizing force (rce of mag female tizing). FIG. 2 is a graph showing the relationship between induction and magnetizing force for an amorphous alloy of the present invention containing an optimal volume fraction of discontinuously distributed crystalline particles. FIG. 3 is a graph showing the relationship between induction and magnetizing force for an amorphous alloy of the present invention containing discontinuously distributed particles in a volume fraction greater than the optimum amount. FIG. 4 is a diagrammatic representation of the alloy of the present invention, showing discontinuously distributed particle groups dispersed in the alloy. The composition of the novel iron-based amorphous alloy preferably consists of 74 to 2 atomic % iron, 8 to 2 atomic % shelf elements, 0 to 16 atomic % silicon, and 0 to 3 atomic % carbon. . Such compositions exhibit enhanced radio frequency magnetism when desensitized according to the method of the present invention. The improved magnetism is
High magnetization, low core loss and low volt-amperedema
nd) is proven. A particularly preferred composition within the foregoing range is 79 atom % iron, 16 atom % shelf elements, 5 atom % silicon and 0 atom % carbon. Alloys processed by the method of the present invention are less than 30% crystalline, preferably about 15% crystalline. High frequency magnetism is improved in alloys possessing a preferred volume percent of crystalline material. The volume % of crystalline material is
Conveniently determined by X-ray diffraction, electron diffraction or transmission electron head microscopy. The amorphous metal alloy is formed by cooling the melt at a rate of about 1 to 1 pC/sec. The purity of all materials may be that found in common commercial products. A variety of techniques are available for fabricating splat quenched foils and ultra-quenched continuous ribbons, wires, sheets, etc. A typical method involves choosing a specific composition and melting and homogeneously blending the desired proportions of powders or granules of the essential elements (or substances that decompose to form the essential elements, e.g. ferroboron, ferrosilicon, etc.). , and the molten alloy is superimposed onto a cooling surface, such as a rotating cylinder.
The magnetic properties of the subject alloys can be increased by dulling the alloy. The method of competitive annealing generally consists of heating the alloy to such a temperature for a time sufficient to induce the precipitation of a discrete distribution of crystalline particles within the amorphous metal matrix. The particle group referred to herein has an average particle size in the range of about 0.05 to lr, and an average intermolecular distance of about 1 to 0 mm,
It has an average volume fraction of about 0.01 to 0.3%. The dampening process is typically performed in the presence of a magnetic field. The strength of the magnetic field is approximately 1 Oersted (80 amperes/
m) to 10 Oersted (800 amperes/machine). However, as previously mentioned, annealing the alloy in the absence of a magnetic field provides superior magnetic properties and reduces manufacturing costs. As seen in FIG. 1, in the absence of discontinuously distributed crystalline particles, the amorphous alloy of the present invention has a high residual magnetization.
square d with netjzation) (Br)
．． c. It was discovered that B shows a daily loop. Hereafter, square d. c. The B-H loop is called type A. This square loop material has a large power loss at high frequencies.
s). when the discontinuously distributed crystalline particle density is at an optimal level, d. c. The B-day loop was sheared (s) with substantially reduced Br, as shown in Figure 2.
heard) shape. From now on, this sheer type d. c. The B-day loop is called type B. Shear loop materials exhibit enhanced low-field permeability and reduced core loss at high frequencies. Typically, the high frequency core loss of shear loop material is about half that of square loop material.
Lower core losses result in less heat buildup in the core, allowing the use of less core material at higher concession levels at a given operating temperature.
If the alloy is phosphoroused to precipitate a volume fraction of discontinuously distributed crystalline particles greater than the optimum amount, d. c.
The B one-day loop has a flat shape with Br close to zero,
The shape will be as shown in Figure 3. From now on, this flat type d. c. Type B daily loop C
It is called. The excitation power required to drive a flat loop material is extremely large, reaching a value of one order of magnitude of the excitation power of a shear or square loop material. At high frequencies, the main component of total iron loss is eddy current loss, which is
It decreases with the ferromagnetic bulk size. By lowering the division size, high frequency iron loss can be minimized. It has been found that controlled precipitation of discontinuously distributed Q-(Fe,Si) particles acting as pinning points of the domamwnils can reduce the dome size. The extent to which the minimum value of iron loss can be reduced according to the present invention depends on the interparticle distance, the volume fraction of the discontinuously distributed particle group, and the particle size of the precipitated phase. The domain size is controlled by the interparticle distance, since the particles act as pinning points for the domain walls. In general, the interparticle distance should be of the same order as the block size. Without the presence of discontinuously distributed particles, the segmentation size would be too large, resulting in excessive eddy currents and iron losses. However, if the interparticle distance is too small, the domain becomes very small, which impedes the wall motion and increases high-frequency iron loss. Preferably, the interparticle distance should be within the range of about 2 to 6 μm.
Similarly, the extent to which the minimum value of iron loss can be lowered is
It depends on the volume fraction occupied by the discontinuously distributed Q-(Fe, Si) particle group in the alloy. As the volume fraction increases above 30%, the soft magnetic properties of the amorphous matrix begin to deteriorate and the crystalline Q-(Fe,Si) grain population provides too much resistance to wall motion. It has been found that it is necessary to adjust the volume fraction of the discontinuously distributed crystalline particles to within a range of about 1-30%. Volume fraction is a function of interparticle distance and particle size. It has been found that the particle size should preferably be within the range of about 0.1 to 0.5 microns. For amorphous alloys containing approximately 78 to 82 at.% iron, 10 to 16 at.% shelf elements, 3 to 10 at.% silicon, and 0 to 2 at.% carbon, a discontinuously distributed crystalline particle population In order to induce the optimal distribution, a circular sample (■r
Oi ship 1, samples), about 0℃~450℃
It should be heated to a temperature of about 13 minutes to 5 hours. The specific time and temperature depend on the alloy composition and quench rate. Fe8, B3.5S3.5C2 and Fe6
, B, 4 Mi, the discontinuously distributed crystalline particles have a star-shaped Q-
(Fe, Si) precipitation. The size of the precipitate is approximately 0.1
It is within the range of 0.3mm to 0.3mm skin. The preferred average interparticle distance d is within the range of about 1.0 to 10 degrees, and about 0.
This corresponds to an optimal volume fraction of 0.01 to 0.15. In order to calculate interparticle distances from electron micrographs, care must be taken to account for the projection of the three-dimensional array onto the two-dimensional image. Applications where low core losses are particularly advantageous include energy storage dielectrics, pulse transformers, transformers for converting modal power supplies, current transformers, etc. As discussed above, alloys annealed by the method of the present invention exhibit improved magnetism that is stable up to about 150 qo. The temperature stability of the alloys of the present invention allows them to be used in high temperature applications. Iron core (cor) made of thematic alloy
When es) are used in electromagnetic devices such as transformers, they demonstrate low power losses, low excitation power demands, etc., thus resulting in more efficient operation of the electromagnetic devices. . Energy loss in the magnetic core as a result of the circulating current through the iron core results in a dissipation of energy in the form of heat. Cores made from the subject alloys require less electrical energy to operate and generate less heat. Even greater savings may be realized in applications where a cooling system is required to cool the transformer core, such as transformers in airplanes or military transformers. Because less heat is generated by a core made from the alloy of the present invention, less cooling equipment is required to remove it. In addition, cores made from the alloys of the present invention have high magnetization and high efficiency, resulting in a reduced weight of iron D for a given capacity class. The following examples are included for a more complete understanding of the invention. The specific techniques, conditions, materials, proportions, reported data, etc. set forth to demonstrate the principles and practice of the invention are representative and should not be construed as limiting the invention. do not have. Example 1 The inner diameter and outer diameter are 0.0397 skin and 0.0, respectively.
445 On the steatite (steati) core of the skin,
Composition F of 0.02 Hirohada width with a weight of approximately 0.030k9
A toroidal test sample was made by wrapping an alloy ribbon of e8,B,3.5Si3.5C2. The alloy was cast into ribbons by rapidly cooling the alloy on a chromium coated copper substrate. A high temperature magnetic wire of 150 evenings was wrapped around the toroid to blunt the moth, 795.
8 amps/d. to skin. c. Created a circumferential field. The sample was heated to 365 qo to 430 qo in an inert gas atmosphere.
At a temperature of qo, for 3 to 2 hours, 795. The pine/rudder field was applied and annealed upon heating and cooling. Average particle size, interparticle distance and volume fraction were determined by transmission electron microscopy. These parameters and 50KHZ, 0.11 power loss and excitation power as a function of the Akyo blunt parameter,
It is listed in Table 1. Table 1 Example 2 Same as described in Example 1 except that the alloy was rapidly cooled on a Cu-Mao substrate with higher conductivity than that of Example 1 and the alloy was cast into a ribbon. A toroidal test sample was prepared using the method. The average grain size, interparticle distance, volume fraction, power loss, and excitation power for the alloy were as shown in Table B. No. U
Table Examples 3 and 4 Annular test samples were quenched into ribbons with alloy compositions of Fe8, B4Si5 (Example 3) and Fe7, respectively.
6Si5 (Example 4) was made in the same manner as described in Example 2. The power loss and excitation power values at 50 KHZ, 0.1 T for these alloys are as shown in Table M (Example 3) and Table W (Example 4) as a function of dawn temperature. . Table IV Example 5 Except that the alloy was cast into ribbons by quenching onto a Cu-Mao substrate, which has a higher conductivity than the substrate of Example 1.
An annular test sample of alloy Fe79BBS was prepared in the same manner as described in Example 1.
s) was created. Also, unlike Examples 1 and 2, the test samples were annealed in the absence of a magnetic field. The microstructural characteristics, namely average particle size, interparticle distance and volume fraction, were maintained substantially identical to those shown in Table W. 50KHZ and 0.1T
The power dissipation and excitation power values of the alloys are shown in Table V as a function of race anchor conditions. Although the present invention has been described in considerable detail as above, it is not necessary to adhere strictly to this detail, and various modifications and improvements will be obvious to those skilled in the art, all of which are within the scope of the claims. It should be understood that these inventions should be included in the scope of the invented invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the relationship between induction and magnetizing force for an amorphous alloy in the absence of precipitated discontinuously distributed crystal grain groups. FIG. 2 is a graph showing the relationship between induction and magnetizing force for an amorphous alloy of the present invention containing an optimal volume fraction of discontinuously distributed particles. FIG. 3 is a graph showing the relationship between yield and magnetizing power for an amorphous alloy of the present invention containing discontinuously distributed particles in a volume fraction greater than the optimum amount. FIG. 4 is a diagrammatic representation of the alloy of the present invention showing discontinuously distributed particle groups dispersed in the alloy. D...Particle diameter,
d... Interparticle distance. FIG. lFIG. 2 FIG. 3 FIG. 4

Claims (1)

[Scope of Claims] 1. An alloy having a composition consisting of 74 to 84 atomic % Fe, 8 to 24 atomic % B, and at least one member selected from the group consisting of the following members (a) and (b): , I 1
6 atomic % or less of Si, (b) 3 atomic % or less of C, (provided that the sum of all alloying elements is 100 atomic %).The alloy has at least 85% of its structure in the form of an amorphous metal matrix. and the alloy has precipitates of crystalline particles of the alloying component discontinuously distributed throughout the amorphous metal matrix, the crystalline particles having a particle size of 0.
Average particle size ranging from 0.05 μm to 1 μm and from 1 μm to 10 μm
An iron-based boron-containing magnetic non-magnetic material having an average interparticle distance in the range of μm, and the particles occupying an average volume fraction of 0.01 to 0.3 with respect to the alloy. Crystalline alloy.
2. The average volume fraction of the crystalline particle group is 0.01 to 0.
15. An alloy according to claim 1 in the scope of claim 15. 3 The average particle size of the crystalline particle group is 0.1 to 0.5μ
An alloy according to claim 1 in the range m. 4
The alloy according to claim 1, wherein the average interparticle distance of the crystalline particle group is in the range of 2 to 6 μm. 5. An alloy having a composition consisting of 74 to 84 atomic % Fe, 8 to 24 atomic % B, and at least one member selected from the group consisting of the following members a and b,
6 atomic % or less of Si, (b) 3 atomic % or less of C, (provided that the sum of all alloying elements is 100 atomic %).The alloy has at least 85% of its structure in the form of an amorphous metal matrix. and the alloy has precipitates of crystalline particles of the alloying component discontinuously distributed throughout the amorphous metal matrix, the crystalline particles having a particle size of 0.
Average particle size ranging from 0.05 μm to 1 μm and from 1 μm to 10 μm
An iron-based boron-containing magnetic non-magnetic material having an average interparticle distance in the range of μm, and the particles occupying an average volume fraction of 0.01 to 0.3 with respect to the alloy. A method for producing a crystalline alloy, wherein an alloy having the above composition is ultra-quenched from a molten state to produce an amorphous alloy having the same composition, and then the obtained alloy is subjected to crystallization of the alloy components in the dispersed state. A method for producing an iron-based boron-containing magnetic amorphous alloy comprising annealing under sufficient temperature and time conditions to produce a discontinuous precipitate distribution of solid particles. 6. The method according to claim 5, wherein the annealing is performed in the presence of a magnetic field. 7. The method according to claim 5, wherein the annealing is performed in the absence of a magnetic field.