JPS6024346A - Ceramic instrument solidified from glassy alloy powder - 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 provides magnetic articles made as cores, pole pieces, etc.
and methods for producing them from metallic glass powder.

Amorphous metal alloys and articles made therefrom are described by Cheno and Bork in US Pat. No. 3,856,513, issued Dec. 24, 1974. This specification teaches certain new alloy compositions which are obtained in an amorphous state and which are superior to previously known crystalline alloys based on the same metal. These compositions can be easily quenched to an amorphous state;
Having desirable physical properties. By ejecting the molten alloy to form droplets and quenching these droplets in a liquid such as water, chilled brine, or liquid chloride, particles of about 10 to 250 μm are produced. It is also described that amorphous metal powders having a diameter can be manufactured entirely.

It is known to produce magnetic articles by aggregating Bacroy and other crystalline alloy powders. New applications requiring improved magnetic properties have simultaneously required efforts to develop alloys and consolidation methods that increase the strength and magnetic response of magnetic articles.

The present invention provides an amorphous alloy powder that is particularly suitable for aggregation into objects with excellent strength and magnetic response. Further in accordance with the present invention there is provided a method of manufacturing a magnetic article in which the aggregation of the vitreous metal powder is carried out using mechanical pressure and/or a binder at an elevated temperature below the crystallization temperature of the material. The present invention also teaches optimal powder dimensions and preferred alloy compositions, suitable binder materials, and post-processing heat treatments.

Articles made by the method of the invention have low core loss and high magnetic permeability. Generally, the solid magnetic glassy metal body has an initial relative permeability of at least about 70 at a frequency of 5 KHz and an induction level of 0.1 Tesla. The term "1 relative magnetic permeability" as used herein shall mean the ratio of the magnetic induction caused by a particular magnetic field in a medium to the magnetic induction caused by the same magnetic field in vacuum. Magnetic compacts are generally produced from powdered glasses or amorphous alloys. A common method for producing glass powders from alloys is a quenching step of the molten alloy followed by fine grinding. 1 with 8,
The manufacture of glassy alloys is described in U.S. Pat. No. 3,856,553.
The resulting sheets, ribbons, tapes, and wires, which can be made according to the teachings set forth in No. 1, in+ (Cheno et al.), are useful precursors for the materials described herein. These amorphous materials H are pulverized as follows.

An amorphous material in the form of a sheet, ribbon, wire or flake is heated above its embrittlement temperature but below its crystallization temperature and mechanically fractured. The resulting flakes and powders of various sizes are sieved to collect flakes and powders of desired size. Another method for obtaining glassy metal alloy powders is described in U.S. Pat. No. 4.29'
No. 0.803 (Ray et al.).

When starting from powder, the aggregation of the powder is the first step in producing the object. Solidifying powders include fine powders (with particle sizes in the range of about 2 to 100 μm), coarse powders (with particle sizes in the range of 100 to 1000 μm), and flakes (with particle sizes of 1000 μm to about 2 fins). diameter)
It may consist of. These flakes and powders are hereinafter simply referred to as powders or powder particles. Consolidation is accomplished by compacting or adhesively bonding the vitreous metal alloy powder.

If low permeability is desired, particle diameters of about 5-10 μm are used. To obtain high magnetic permeability, larger particle diameters of about 180 μm or more are used. The combination of relatively high magnetic permeability (e.g., on the order of about 200 at 5 KHz and 0.1 Tesla induction) and excellent mechanical hardness (e.g., on the order of about 400 ky/J) makes it possible to obtain a magnetic material with a mesh size (US sieve) of about 80. This is achieved through the use of particles. The flake core uses larger particles with parallel planes. The properties in this case approach those of a lamellar core.

For consolidation, the powder is placed in an evacuated can and hot rolled at a temperature below the glass transition temperature of the alloy, or hot compacted at equilibrium to the desired shape. Additionally, the powders can be conventionally hot compacted below their glass transition temperature in vacuum, air, or other protective atmosphere into any desired shape. Preferably, the powder is compacted at a pressure of at least 7 MPa at a temperature between 85 and 95 degrees above the glass transition temperature. It is also possible to obtain compacted amorphous shape densities close to the theoretical maximum with short compaction times using high pressures and temperatures. The effects of time, temperature and pressure on compressed density are shown in Table 3. The relative density will increase as the temperature increases to the glass transition temperature and as the pressure increases. By using high pressures and temperatures near the glass transition temperature, compression times can be reduced by a fraction of a second.

Correlation of compression time, temperature, pressure and density for Fe 7 BB□a S 1 g glassy alloy (+80 mesh powder ax) molded into a toroid with an outer diameter of 4.15 crn and an inner diameter of 2.25 cm. Compression temperature Pressure Density *810 400
52.0 78.7 20 400 520 80.4 30. 400 210 70.9 30 400 310 77.2 30 400 420 8L1.2 30 400 520 85.2 30 425, 520 90.6 * Powder size, 80 mesh or more ** 100 mesh is 7.2? /cr;1 The powder can be mixed with a suitable organic binder (such as Hatafine) and then cold pressed into the appropriate shape. Insulators and binders include W resins, such as phenol formaldehyde resins, and Bakelite (Union).
Carbide Co., Ltd.'s open cap) is used. Other suitable binders include synthetic oils, dry oils, distillation residues of oils or fats, solutions of gums or resins, and oxidized oil or wax compounds. Certain oxides, such as S
iO2lMgO and B2O3 can be mixed with a powder and the mixture can be consolidated under pressure at an elevated temperature below the glass transition temperature or crystallization temperature of the powder. Certain acids, such as borates, can be mixed with the powder and the mixture consolidated under pressure at an elevated temperature below the glass transition or crystallization temperature of the powder. In this case, certain oxides (
For example, borate decomposes into B203) and water (which evaporates during coalescence). The amount of binder is about 60% by weight, preferably less than 10% by weight for high permeability cores, more preferably 0.1 to 4% by weight. Such shaped alloys have a theoretical maximum of at least 6
It can have a density of 0.

The compacted object can be cured at relatively low temperatures, below the glass transition temperature, to provide greater strength and then ground to final dimensions. Preferred products from this method have a shape suitable for magnetic components.

The hardening process can be performed while simultaneously applying a magnetic field.

Preferably, the curing process is carried out in the absence of oxygen. These treatments are matched to optimal heat treatment cycles to obtain the desired magnetic and structural products made from glassy metal alloys.

After compaction, the final product is ground to final dimensions.

This process is suitable for fabricating large engineering equipment with simple geometric shapes. Additionally, the final product can be annealed if desired depending on the particular alloy used in the application at hand. The solid body has a density not less than about 60% of the as-formed alloy, preferably 95%.
It has a density of

Metallic glasses are molten alloy products that have been cooled to a rigid state without crystallization. Metallic glasses of this type generally have at least some of the following properties: High hardness and scratch resistance, great vitreous surface smoothness, dimensional and shape stability, mechanical stiffness, strength, ductility, high electrical resistance compared to related metals and their alloys, excellent magnetic flexibility 5offtness) and X-ray diffraction pattern.

The word "alloy" is used here in its ordinary sense to denote a solid mixture of two or more metals (Abridged Chemistry Dictionary, 9th edition, Van Nostrand Reinhold, New York, 1977). ). These alloys further contain at least one non-metallic element. The terms "glassy or vitreous metal alloy"-6 metallic glass, and "amorphous metal alloy" are all considered interchangeable as used herein.

Alloys suitable for the method of the invention include those of the composition MaM'bZ c. In the formula, when M is at least one of Fe, Ni and Co, M' is Cr, Mo, W
,V.

2 is at least one of Nb, Ta, Ti, Zr and Hf; 2 is at least one of B, Si, C and P; 'a', b' and 'Cn are atoms; ), a + c = 100, and a is approximately 65 to 8
8, b ranges from about 0 to 7, and C ranges from about 12 to 28.

Preferred ferromagnetic alloys according to the invention are those based on members of the group consisting of iron, cobalt and nickel.

Iron-based alloys have the general composition Fe 40-88 (C
o At least 1a) of yNl. -48(Cr,
Mo, W, V, Nb, Ta, Ti, Zr
, Hf). -7(B, St, C
, P) 12-28 (numbers in the legs are in atomic relation); cobalt-based alloys have the general composition Co 4 g , , B 8 (at least one of Fe , Ni) (Cr, Mo, W, V, Nb.

-40 At least one of Ta, Ti, Zr, Hf) g-7
(B.

At least one of Si, C, and P) -22
8 (values on legs are in atomic %): Alloys based on nickel have a general composition of N1 (at least 0-6 of Co t Fe).
8 also I Fii ) 2 o46 (Cr , Mo , w
, v, Nb , Ta , Ti yZr )Hf). -7 (13, at least one of Si vcpP) (number of legs is 2-28 atoms).

A preferred alloy is 5 atoms or less of carbon, 25 atoms of boron,
It has an atomic ratio of 20 atoms of silicon and 10 atoms of phosphorus.

During compaction, each powder is subjected to a different degree of external stress.

This external stress changes the magnetic properties of the powder if it is magnetostrictive. Therefore, it is desirable to consolidate powders with low saturation magnetostriction. This is especially true for cohesive materials for use at high frequencies. Saturation magnetostriction λ8 is related to the fractional change in length Δ1/1 that occurs in a magnetic material when going from a demagnetized state to a saturated ferromagnetic state. Magnetostriction (a unitless quantity) is often referred to as microstrain (mi
(i.e. microstrain is the fractional rate of change in length in lppm). The quantity λ8 is positive or negative and is determined depending on the material whose soft magnetism is strongly influenced by this quantity. The preferred absolute value of λ for powders is approximately 10×10
(i.e. below 10 ppm), which accounts for most of the glassy alloy powder based on cobalt and nickel, as well as about 40 atoms of iron and Cr, Mo, W, V,
At least one element selected from the group consisting of Nb, Ta, Ti, Zr and Hf, or about 40 to 88 atoms of iron, Cr, Mo, W, V
It is found in iron-based vitreous alloy powders containing two or more atoms φ of at least one element selected from the group consisting of +Nb, Ta, Ti, Zr, and Hf. Most preferred λ for powder.

The value of is almost zero or zero, which is about 0.06
This is achieved in a cobalt-based vitreous alloy powder with an iron to cobalt content ratio in the range of ˜about 0.16. If magnetostriction is not an important factor, as is the case in most low frequency applications (ie in the 50/60 Hz region), there is no need to consider these.

Amorphous metal powder can be compressed into parts suitable for various uses, such as electromagnetic cores and pole pieces. The vitreous compacted material has high magnetic permeability.

These may contain much less nickel than ordinary compression alloy bodies of comparable magnetic permeability. The obtained core can be used as a transformer core for freezing or other alternating current applications.

The following examples are presented in order to more fully understand the invention. The specific techniques, conditions, materials, proportions, and data reported to illustrate the principles and practice of the invention are illustrative and should not be construed as limiting the scope of the invention.

Example 1 An amorphous metal powder having dimensions of a few millimeters or less was prepared consisting of an alloy having a composition of Fe78B□381 g.

These powders were sieved and those with different dimensions were sorted. The sieved powder is compressed to an inner and outer diameter of approximately 3.2 crn and 4.2 α, respectively, and a height of approximately 0.
．． It was made into a torus of 7 strokes. The temperature and pressure of consolidation were 350° C. and 345 MPa, respectively. The influence of powder dimensions on the magnetism of as-formed and annealed toroids is summarized in Table 3. This table shows that larger powders tend to give better magnetism, with 180 μT
A powder size of rL ~ 1.4 m is shown to be most preferred to obtain the best overall magnetism. For example, about 80μrI
Annealed tori produced from powders with dimensions in the order of L~1.4 have magnetic permeabilities of over 200 and 70 at 5 x nz and 50 KI (z, respectively).

Example 2 In Table H, it is observed that the magnetic permeability μ(f) of the torus decreases as the frequency f increases. This is due to eddy current losses caused by conductivity between the powders. This conductivity is of Kana 9 since each powder particle is not insulated. In general, eddy current losses in metallic ferromagnetic materials increase with frequency, the dimensions of the material, and its conductivity. Therefore, reducing particle size and powder conductivity will reduce eddy current losses. Powder quantity Fe78B□a S 1 of various dimensions to increase electrical resistance (opposite of conductivity)
The influence of Si0□2 weight t% mixed with g powder on the magnetism of the unified core is summarized in Table 3. For cores made from powders larger than 180 μm, 75 wt% borate was also used to investigate the effect of different insulation properties. Borate is boric acid, which decomposes into boron oxide and provides an excellent binder and insulation between powder particles. As the results in Table ■ show, the insulation provided by SiO□, or boron oxide, was indeed effective in improving high frequency magnetism. However, what was unexpected was that the larger powder size was better. As a result, a good magnetic property was obtained.

For example, the magnetic permeability μ for a core made from insulating powder with dimensions of 180 μm or more at 50′ KHz and 0.1 T induction is approximately 16 o″″C. Dimensions 68
tt (5
0KHz, 0.1T) = 42. Therefore, the size of the insulating powder is preferably about 180 μm or more in order to achieve good magnetism in the compressed core of the present invention.

Table ■ Powder quantity insulation manufactured under the same conditions as in Table ■ f = 5KHz
f=50KHz -≧180μm 7.5wt% volley) 3<SO13
0) 180 μm 2% by weight Si0 340 160-
2 180 μm ~ 2 wt% Si0 210 130500
μm 125μm ~ 2wt% Si0 130 75180μ
m 66μm~125μm 2wt%si0 11Q 65<38μ
m 2 wt % SiO7242□ 2 Example 6 A number of cores were made from powders of various sizes insulated with 81022 wt % or borate 7,5 wt %. The range of magnetism obtained in annealed cores made from powders with dimensions up to 75 .mu.m and from 180 .mu.m to 1.4 .mu.m is shown in Table 1. The overall properties of cores made from larger powders were better than those made from smaller powders. 5KHz and L]
, low core loss (L) of 10W/ky in IT
It is noteworthy that a high magnetic permeability (μ) of 1000 and 1000 was achieved in a Fe-based powder core with a saturation induction of about 1.6 Tesla. These values are approximately 0.5
This should be compared to commercially available Ni-Zn ferrites with Tesla saturation induction tt (5 KHz, 0.IT) of about 1000 and L of about 5 W/Kg.

Table tV From Fe78B□3Si9 powder at 350°C for 5 hours, about 6
Magnetic range obtained for cores united at a pressure of 45 MPa. The powder particles were insulated with 5iO22% by weight or 7.5% by weight. The cores were annealed for 2 hours at 400° C. in a DC magnetic field of about 1600 A/m applied along the circumference of a torus having the dimensions indicated in the heading of Table 3.

DC coercive force (W/Ni) <75μm ~30-15090-500 20-10
0180μm -40-120100-100020-
401,4Tcn Example 4 The performance of a ferromagnetic material will be greatly affected by its magnetostriction (λ), Qk, depending on the magnitude of the magnetochemical action. The amount of λ introduces additional magnetic anisotropic energy due to internal stress. Compressing magnetic powders places each powder under a different degree of stress. If the powder is magnetostrictive, this external stress increases the total coercive force, changes its remanence, and thus affects the AC properties of the core. Table■
The relationship between the magnetostriction value of a powder material and the AC characteristics of a core compressed from powder of similar dimensions is shown in Figure 11. This table clearly shows that powder cores with lower magnetostriction exhibit better magnetic properties. Therefore, a low magnetostriction of about 10.times.10@-6 or less is preferred, and the most preferred value of .lambda. is approximately zero to obtain the best overall magnetism of the compressed core of the present invention.

Table V Effect of magnetostriction of powder materials on the properties of united cores made from powders with dimensions between 180 μm and 1.4 mm. The compression conditions are shown in the title of 2.

Composition λ (10-6 N (W/ky) S 13 , 5
C2 Fe7sBtaSic+ 30 220 701° To 4... 9 6! :) 0 22 Mo 4B I B MO2B□5Si5 Example 5 To further improve the magnetism of the compressed core of the present invention manufactured from the powder with low magnetostriction shown in Table ■, 5iO24% by weight and Mg04% by weight were added. to insulate the powder particles. The results are shown in Table ■. Comparing the data in Tables ■ and ■, it is clear that the insulated, low magnetostrictive powder core exhibits the best overall magnetism. Magnetic permeability Cμ) 800 to 16'00 at 5 KHz and 0.1 Tesla is Ni
-Zn is comparable to or better than mono (μ~1000).

Insulated low magnetostriction Fe with dimensions 180 μm to 1.4 tone
4oN13 BMo 4B I B (λ:9X1[
1-6) and co7□, 2Fe5.8M02B15S
Magnetism of cores made from i5(λ~o). The core unity condition is the same as the one shown in the title of Table ■. The core is given along the circumference of the torus 1 600 A
Annealed at 650 °C for 2 h under a magnetic field of /m.

Although the present invention has been described in considerable detail above, it is not necessary to adhere to these detailed descriptions, and it is obvious that various modifications can be made by a person skilled in the art, all of which are included within the scope of the claims. be done.

Patent Applicant: Allied Corporation Procedural Amendment July 2s, 1932, Showa β, Patent Application No. /-! 7 Yu,? / No. 2, name of invention
! '72nono;False't@z$6, Relation to the case of the person making the amendment Patent applicant's address (required name: Ding Kui I), Koo 0V-John 4, Agent

Claims (10)

[Claims] (1) A method for producing a shaped magnetic metal alloy article comprising compressing ferromagnetic vitreous metal powder having a particle size of about 2 μm to about 2 fins into a solid body. (2) SiO□, TaoO and B are added to the powder before the compression process.
2O3, and the amount of binder present in the mixture is about 1 to 2.
A method according to claim 1, in the range of 0% by weight. (3) The method according to claim 2, wherein the powder has a composition essentially consisting of the following formula: %. (4) Essentially the following formula % (where M is Cr, Mo, WtV, Nb, Ta,
At least one of the following elements: Ti, Zr, Hf, ZtiB, and Si. A unified ferromagnetic vitreous metal body consisting of a vitreous alloy having a composition defined by at least one of the elements C and P. (5) an annealed ferromagnetic glassy metal body consolidated from powder having a particle size between about 180 μm and 1.4 μm;
a ferromagnetic glassy metal body 1 having a composition of Fe7BB□351 g and having an initial relative permeability of at least about 70 at 5 KHz and 0.1 Tesla induction; (6) An annealed ferromagnetic vitreous metal body consolidated from powders with a particle size of about 180 μm-1,4 van, the glassy metal body having a composition of Fe7BB□381 g, 5 KHz and A ferromagnetic glassy metal body having an initial relative permeability of at least about 100 at an induction of 0.1 Tesla. (7) an annealed ferromagnetic vitreous gold body consolidated from powder with a particle size between about 180 μm and 1.4 μm,
A ferromagnetic glassy metal body having a composition of Fe4oN1asMO4B□8 and having an initial relative permeability of about 650 and a core loss of about 22 W/kg at 5 KHz and 0.1 Tesla. (8) An annealed ferromagnetic glassy metal body consolidated from powder having a particle size of about 180 μm to 1.4Ta, the glassy metal body being Fe46N13BMO4
A ferromagnetic glassy metal body having a composition of B□8, with an initial relative permeability of about 1600 at 5 KH2 and an induction of 0.1 Tesla and a core loss of about 6 W/7. (9) A ferromagnetic vitreous metal body consolidated from powder having a particle size of about 18 l to 1.4 mm, and this vitreous metal body is composed of CO72,2F e s , aMo 2 B
Composition of 15 S 1 s, 5 KHz and 0.
A ferromagnetic glassy metal body having an initial relative permeability of about 800 and a core loss of about 19 W/7 at an induction of 1 Tesla. (10) An annealed ferromagnetic glass wire mesh body aggregated from particles having a particle size of about 180μrIL to 1.4Nm, the glassy metal body having co7□, 2Fe5.8
It has a composition of M02B15S15 and has a frequency of 5 KHz and 0
．． A ferromagnetic glassy metal body with an initial relative permeability of about 900 and a core loss of about 3 W/kg at 1 tare and 7 leads.