Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3856513 A
Publication typeGrant
Publication dateDec 24, 1974
Filing dateDec 26, 1972
Priority dateDec 26, 1972
Also published asCA1012382A1, DE2364131A1, DE2364131C2, DE2366326C2, DE2366327C2
Publication numberUS 3856513 A, US 3856513A, US-A-3856513, US3856513 A, US3856513A
InventorsChen H, Polk D
Original AssigneeAllied Chem
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Novel amorphous metals and amorphous metal articles
US 3856513 A
Abstract
Novel metal alloy compositions which are obtained in the amorphous state and are superior to such previously known alloys based on the same metals are provided; these new compositions are easily quenched to the amorphous state and possess desirable physical properties. Also disclosed is a novel article of manufacture in the form of wire of these novel amorphous metal alloys and of other compositions of the same type.
Images(6)
Previous page
Next page
Description  (OCR text may contain errors)

United States Patent [191 Chen et a1.

[ Dec. 24, 1974 NOVEL AMORPHOUS METALS AND AMORPHOUS METAL ARTICLES [75] Inventors: Ho-Sou Chen, Warren; Donald E.

Polk, Morristown, both of NJ.

[73] Assignee: Allied Chemical Corporation, New

York, NY.

[22] Filed: Dec. 26, 1972 [21] Appl. No.: 318,146

[56] References Cited UNITED STATES PATENTS 3,403,996 10/1968 Hirota et al 75/124 X 3,406,057 10/1968 Hirota et a1 75/170 X 3,427,154 2/1969 Mader 3,433,630 3/1969 Hirota 3,461,943 8/1969 Schile r.

3,542,542 11/1970 Hirota 3,543,831 12/1970 Schile 3,658,979 4/1972 Dunn et al. 164/82 Primary Examiner-L. Dewayne Rutledge Assistant Examiner-Arthur J. Steiner Attorney, Agent, or Firm-Arthur J. Plantamura [5 7 ABSTRACT Novel metal alloy compositions which are obtained in the amorphous state and are superior to such previously known alloys based on the same metals are provided; these new compositions are easily quenched to the amorphous state and possess desirable physical properties. Also disclosed is a novel article of manufacture in the form of wire of these novel amorphous metal alloys and of other compositions of the same type.

8 Claims, N0 Drawings NOVEL AMORPHOUS METALS ANI) AMORPHOUS METAL ARTICLES BACKGROUND OF THE INVENTION This invention relates to novel amorphous metal compositions and to the preparation of wires of these and other amorphous metal alloys.

Heretofore, a limited number of amorphous, i.e., noncrystalline or glassy, metal alloys have been prepared. To obtain the amorphous state, a molten alloy of a suitable composition must be quenched rapidly, or alternatively, a deposition technique must be used: suitably employed vapor deposition, sputtering, electrodeposition, or chemical (electro-less) deposition can be used to produce the amorphous metal.

The production of amorphous metal by these known techniques, i.e., either through a rapid quench of the melt or by deposition, severely limits the form in which the amorphous metal can be obtained. For example, when the amorphous metal is obtained from the melt, the rapid quench has generally been achieved by spreading the molten alloy in a thin layer against a metal substrate such as Cu or Al held at or below room temperature. The molten metal is typically spread to a thickness of about 0.002 inch which, as discussed in detail by R. Predecki, A. W. Mullendore and N. J. Grant .in Trans. AIME 233, I581 (1965) and R. C. Ruhl in Mat. Sci. & Eng. 1,313 (1967), leads to a cooling rate of about l C/sec.

Various procedures have been proposed to provide rapid quenching by spreading the molten liquid in a thin layer against a metal substrate. Typical examples of such techniques are the gun technique of P. Duwez and R. H. Willens described in Trans. AIME 227, 362 (1963) in which a gaseous shock wave propels a drop of molten metal against a substrate made of a metal such as copper; the piston and anvil technique described by P. Pietrokowsky in Rev. Sci. Instr. 34, 445 (1963) in which two metal plates come together rapidly and flatten out and quench a drop of molten metal falling between them; the casting technique described by R. Pond, Jr. and R. Maddin in Trans. Met. Soc.

AIME 245, 2475 (1969) in which a molten metal stream impinges on the inner Surface of a rapidly rotating hollow cylinder open at one end; and the rotating double rolls technique described by H. S. Chen and C. E. Miller in Rev. Sci. Instrum. 41, I237 (1970) in which the molten metal is squirted into the nip of a pair of rapidly rotating metal rollers. These techniques produce small foils or ribbon-shaped samples in which one dimension is much smaller than the other two so that their usefulness as a practical matter is severely limited. Because of the high cooling rates necessary to obtain the amorphous state from quenched liquid alloys, it is required that the amorphous metals be formed in a shape which does not preclude adequate quenching, i.e., they must have at least one dimension small enough to permit the sufficiently rapid removal of the heat from the sample.

Metal alloys which are most easily obtained in the amorphous state by rapid quenching or by deposition techniques are mixtures of transition metals with metalloids, i.e. semimetals. In each case, the alloy is approximately 80 atomic percent transition metal and atomic percent metalloid. Examples of alloys of this type reportedly made previously in the amorphous State are Pd34SI15, Pd79Sl2 pdn cugsl C080P20,

76.9 1a.Ss 9.4s tl1.4 lK.fi li0 lIl 7 l5 ll0 25 42.s 42.5 is t5 l0 75 l5 10v so mn and Ni B where the subscripts indicate atomic percent.

The cooling rate necessary to achieve the amorphous state, i.e., to avoid crystallization, and the stability of the amorphous state once it is obtained depends upon the composition of the alloy. Some of these alloys are better glass formers than others; these better" alloys can be obtainedin the amorphous state with a lower cooling rate, which in practice may be more readily obtainable, or can be obtained with a greater thickness when quenched from the melt with a given technique.

Generally, there is a small range of compositions surrounding each of the known amorphous compositions where the amorphous state can be obtained. However, apart from quenching the alloys, no practical guideline is known for predicting with certainty which of the multitude of different alloys will yield an amorphous metal with given processing conditions and hence which of the alloys are better" glass formers. v

The amorphous and the crystalline state are distinguished by the respective absence or presence of long range periodicity. Further, the compositional ordering in alloys maybe different for the two states. These differences are reflected in the differences in their x-ray diffraction behavior, and accordingly, x-ray diffraction measurements are most often used to distinguish a crystalline from an amorphous substance. Diffractometer traces of an amorphous substance reveal a slowly varying diffracted intensity, in many respects similar to a liquid, while crystalline materials produce a much more rapidly varying diffracted intensity. Also, the physical properties, which depend upon the atomic arrangement, are uniquely different for the crystalline and the amorphous state. The mechanical properties differ substantially for the two states; for example, a 0.002 inch thick strip of amorphous Pd si is relatively more ductile and stronger and will deform plasticallyupon sufficiently severe bending while a similar crystalline strip of the same composition is brittle and weak and will fracture upon identical bending. Further, the magnetic and electrical properties of the two states are different. In each case, the metastable amorphous state will convert to a crystalline form upon heating to a sufficiently high temperature with the evolution of a heat of crystallization.

It should be noted, moreover, that cooling a molten metal to a glass is distinctly different from cooling such a molten metal to the crystalline state. When a liquid is cooled to a glass, the liquid solidifies continuously over a range of temperature without a discontinuous evolution of a heat of fusion. In contrast, crystallization is a thermodynamic first order transition and thus is associated with a heat of fusion and a specific temperature.

SUMMARY OF THE INVENTION An object of the invention is to provide a novel amorphous metal compositions which are readily quenched to the amorphous state, have increased stability, and possess desirable physical properties.

A further object of the invention resides in the provision of articles of manufacture of these novel amorphous metals in a variety of forms, e.g., ribbons, sheets, wire, powder, etc.

Another object of the invention is to provide an arti ole of these and other amorphous metal compositions in the form of wire, i.e., a filament with a cross-section which is approximately circular, i.e., a rod-like filament, as contrasted with strands which are ribbon like.

Additional objects and advantages will become apparent from the description and examples provided.

The novel compositions of interest in this invention are composed primarily of Fe, Ni, Cr, Co, and V. Although certain compositions, i.e. Fe P C Fe P C Fe P B Co P B Fe B C and Ni P B have been previously described as being quenched from the melt to the amorphous state, we have discovered that certain novel, distinct and useful compositions may be obtained by the addition of small amounts, i.e., from 0.1 to 15 atomic percent but preferably from 0.5 to 6 atomic percent, of certain elements such as Al, Si, Sn, Sb, Ge, In, or Be, to such alloys. As a consequence of the introduction of these elements, these alloys become much better glass formers, i.e., the amorphous state is more readily obtained and moreover, is more thermally stable.

We have found that the inclusion of small amounts of certain elements of a group hereafter sometimes referred to by the symbol Z, and consisting of Al, Si, Sn, Ge, ln, Sb or Be, in amounts of from about 0.1 to about 15 atomic percent, to alloys of the type wherein M is a metal selected from one or more of the group consisting of Fe, Ni, Co, V and Cr; and Y represents elements from the group'consisting of P, B, and C; (k) and (p) are in atomic percent and are about 70 to 85 and about 30 to 15, respectively, provides superior glass forming alloys. Illustrative alloys, for example, are Fe P, C Si,Al Fe Ni P, B Al Ni P B Ab, and Cr, .-,Co Ni P, B Al and may have the general formula:

wherein M, Y, and Z are as defined above and a, b, and c are in atomic percent and range from about 60 to 90, about 10 to 30 and about 0.1 to 15, respectively, and a plus b plus c equals 100.

Additionally, we have discovered that the alloy Fe Ni P B and those alloysof similar compositions (e.g. Fe Nl35P13B7C FE40Ni P B Fe3oNl5 P B are SU- perior glass forming alloys.

Selected alloys of the kinds disclosed above may be relatively more consistently and more readily quenched to the amorphous state than previously thought possible with known Fe-Ni-Cobased alloys. Moreover, these alloys are more stable; upon heating, they show the thermal manifestation of the glass transition (a sudden increase in the specific heat) while previously known Fe-Ni-Cobased alloys do not. Typically, amorphous alloys which show this thermal manifestation of the glass transition are more readily obtained in the amorphous state than amorphous alloys which do not.

The compositions within the contemplation of the present invention can be obtained in the form of ribbons or strips using the apparatus described in the above-mentioned references, Pondand Maddin, or that of Chen and Miller, or other techniques which are similar in principle. Further, wider strips or sheets can be obtained with similar quench tenchiques when the molten metal is squirted as a sheet, for example, rather than with an approximately round cross section. Additionally, powders of-such amorphous metlas where theparticle size ranges from about 0.0004 to 0.010 inch can be made by atomizing the molten alloy to droplets of this size and then quenching these droplets in a liquid such as water, refrigerated brine, or liquid nitrogen.

The alloys discussed above in each case are made from the high purity elements. however, in the utilization of these alloys, it is anticipated that the alloys would be made from the less expensive commercially available material which would have small amounts of other elements in solution. Thus the alloys contemplated by the'invention may contain fractional amounts of other elements which are commonly found in commercially available Fe or Ni alloys, for example, either as a result of the source of the primary metal or through a later addition. Examples of such elements are Mo, Ti, Mn, W, Zr, Hf and Cu.

In addition to the novel amorphous compositions described herein, the invention contemplates a novel article of manufacture in the form of amorphous metal wires of these alloys and others of the transition metalmetalloid type. In providing the wire-form article, a stream of molten metal is formed by squirting the molten metal from a nozzle or otherwise forming a jet from a suitable die and appropriately quenching the alloy.

Suitable compositions from which such wires are made may be represented by the general formula wherein T is a transition metal or mixture of said transition metals and X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, beryllium and antimony and mixtures thereof and wherein i and j are atomic percent and range from about to 87 and from about 13 to 30, respectively. It will be understood that not every alloy encompassed within the formula T X will necessarily yield an amorphous product. For example, a given composition may form a crystalline wire with a particular quenching technique and diameter, while an amorphous wire may be formed with a different quenching technique which provides a higher cooling rate and/or with a smaller diameter. Addition ally, some specific ratios within the general formula T X,- cannot be quenched from the melt to a wire of diameter large enough to be useful.

While most metal wire is conventionally prepared by drawing the metal through successively smaller dies, such a technique is not appropriate in the production of wire of amorphous metals. Amorphous metals, because of the manner in which they must be obtained, are not available in the form and dimensions required ofthe starting materials which are to be drawn to wires.

The quenching of the molten jet to form an amorphous metal wire has been achieved by squirting the molten jet into stationary water or refrigerated brine. however, any process may be used to quench the molten jet to the amorphous state as long as the cooling rate is great enough to avoid crystallization and disruption of the molten jet from the wire form does not take place during cooling. The cooling rate experienced by the molten metal stream or jet during quenching is dependent upon both the technique used to cool the molten jet and the diameter of the jet; the cooling technique determines the rate at which heat is removed from the surface of the jet while the diameter determines the surface-to-volume ratio and hence the quantity of heat which must be removed per unit area to reduce the temperature a given amount. As noted heretofore, different compositions require different minimum cooling rates in order to obtain the amorphous state. Thus, in order to obtain an amorphous, as distinguished from crystalline, metal wire, the cooling technique, the jet diameter, and the alloy composition must be reconciled.

The amorphous metal wire contemplated by the invention may be derived from a range of compositions of the transition metalmetalloid type alloys including the novel compositions described above, previously inown amorphous compositions, from which wire form articles have not previously been prepared, as well as from other alloy compositions of the type T,-X,.

The production of amorphous metal wires yields a number of advantages because of their unique properties which are not possessed by crystalline metal wires produced by ordinary techniques. For example, glassy metal wires are less sensitive than crystalline wire to radiation damage and have a small or even negative temperature coefficient of resistivity. In preparing the novel amorphous alloy compositions of the invention, important processing economies are also available; the amorphous wire form of certain compositions may be less expensive for the sizes and strengths which can be obtained than the commonly used drawn wire. The amorphous metal strands, wires, sheets, etc., contemplated by the invention, find a variety of uses such as reinforcement use, e.g. as tire cord or as reinforcement in molded thermoplastic or thermosetting plastics; as filter media; biomedical reinforcement, e.g. sutures; as relay magnets; corrosion resistant chemical processing equipment; and the like.

Typically, in accordance with the invention, wires of about 0.005 inch diameter are formed, although the invention is not restricted to such diameter. Additionally, these alloys are ideally suited for the melt spinning of wire since they are generally of a near-eutectic composition and hence have a relatively low liquidus temperature, i.e. the lowest temperature at which the alloy is totally liquid in equilibrium. This simplifies the processing of the alloy and expands the list of materials which can be used to contain the molten alloy and as nozzles or dies to form the molten stream. For example,

Fe P QAh, which is 86.7 weight percent Fe, has a liquidus temperature of about 1020C while pure Fe melts at ,1535C..

Various processes can be used to achieve the necessary cooling to yield the amorphous alloys. As stated above, the stream of the molten jet may be squirted into stationery water or refrigerated brine and appropriately collected therefrom after it is quenched. Typical of other specific processes which may be adapted to produce amorphous metal wire in accordance with the invention include that process described by S. Kavesh in a copending U.S. Pat. application, Ser. No. 306,472, filed Nov. 14, 1972; those by R. D. Schile in U.S. Pat. Nos. 3,461,943 and 3,543,831; and that described by S. A. Dunn, et al. in U.S. Pat. No. 3,658,979. While these same methods may be employed to yield either crystalline or amorphous metal, one skilled in the art would experience no difficulty in accordance with the teaching presented herein regarding the use of appropriate cooling rates, wire diameters and compositions so as to obtain an amorphous metal wire.

These amorphous alloys and wire form articles have very desirable physical properties. For example, high tensile strengths and a high elastic limit in the asquenched state can be achieved as well as good corrosion resistance and unique magnetic properties in various selected compositions. Also, a number of compositions are found to be remarkably ductile in the amorphous state. Some specimens, for example, can be bent over radii of curvature less than their thickness and can be cut with scissors. Also, with these ductile samples, tensile strengths of up to 350,000 psi have been obtained in the as-quenched condition. Thus, the heat treatments often given crystalline materials to obtain high strength are obviated with the amorphous metal alloys. Alloys such as Fe P, .-,C,B,Si,Al can be quenched directly from the melt to form inexpensive, high strength wire which can be employed directly as a commercial product.

The amorphous alloys provide strong, corrosionresistant material; selected compositions of these amorphous alloys are relatively unreactive with concentrated surfuric, hydrochloric, or nitric acid. For example, amorphous Feg Ni P B Al is found to be several orders of magnitude less reactive than stainless steels with concentrated hydrochloric acid.

Further, it has been found that various of the metal alloys of the same general formula T,X,- considered above also have the desirable properties of high strength and hardness, ductility and corrosion resis tance even when they are partially crystalline. The fraction of the sample that is crystalline can be estimated by suitably employed x-ray or electron diffraction, electron transmission microscopy, and thermal analysis. Hence, the invention thus also contemplates a metal wire which is partially crystalline but which is at least 50 percent amorphous. For example, such wires may be rendered partially crystalline because the quenching rate is lower than that required to obtain the totally amorphous state for the specific composition being quenched.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Typically, the preferred novel amorphous compositions of the invention are those characterized by the formula M Y Z wherein M is a metal selected from the group consisting of iron, nickel, cobalt, chromium and vanadium and mixtures thereof; Y is an element selected from the group consisting of phosphorus, boron and carbon, and mixtures thereof; and Z is an element selected from the group consisting of aluminum, antimony, beryllium, germanium, indium, tin and silicon and mixtures thereof and wherein the relative proportions in atomic percentages range from about to 80, b from about 19 to 22, and c from 1 to 3.

These metals offer a variety of characteristics which may make them suitable for a wide range of special applications. For example, amorphous alloys in which M is totally or primarily iron, e.g. Fe P C Si Al are of particular interest because of their low cost and relatively high strength. Amorphous alloys such as Ni Fe P B Al are of significance, for example, because of their special ease of formation in combination with high strength and corrosion resistance. Alloys which have a high chromium content, e.g. Cr P B Si are exceptional in their hardness and corrosion resistance.

The wire form amorphous metal alloy products of the invention include the amorphous alloys defined by the formula (I) hereinabove and contemplates also wire form products of other amorphous metals as well and may be defined as those alloys having the formula wherein T is a transition metal or mixture thereof and X is an element selected from the group consisting of aluminum, antimony, beryllium, boron, germanium, carbon, indium, phosphorus, silicon and tin and mixtures thereof and wherein the proportion in atomic percentages as represented by i andj are respectively from about 70 to about 87 and from about 13 to about 30 with the proviso that i plusj equals 100. The transition metals T are those of group 18, 111B, IVB, VB, VIB, V118 and VIII of the Periodic Chart of the Elements and include the following: scandium, yttrium, lanthanum, actinium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium,osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold; preferably Fe, Ni, Co, V, Cr, Pd, Pt and Ti.

The amorphous metal wires of composition T,-X are typically from 0.001 to 0.020 inch in diameter, with diameters of 0.004 to 0.008 inch being preferred. Any suitable technique which cools the molten jet sufficiently fast to avoid crystallization or jet breakup can be used to quench the jet. The simplest such method is to squirt the molten metal stream into a'suitably chosen liquid such as water or iced brine. An advantageous technique is that described in the copending application of S. Kavesh, Ser. No. 306,472, filed Nov. 14, 1972, in which the molten jet is quenched in. a concurrently flowing stream of liquid. The novel compositions and article of the invention are not limited by this process, however, since various other processes which provide appropriate quenching conditions may be utilized, such as the processes described by R. D. Schile in US. Pat. Nos. 3,461,943 and 3,543,831, in which the cooling of the molten jet through corona discharge, gas jets, and/or the deposition on the stream of a colder substance are used.

The invention will be further described by the following specific examples. It will be understood, however, that although these examples may describe in detail certain preferred operating variables and proportions within the contemplation of the invention, they are provided primarily for purposes of illustration and the invention in its broader aspects is not limited thereto. Parts stated unless otherwise expressed are atomic percent.

EXAMPLE 1 Elemental Fe, P, C, Si and A1 are weighed so that the product mixture yields the following alloy: Fe P, C Al Si,. The Fe, P and C were sintered for 1 day in an evacuated sealed fused silica tube at 450C, then melted in vacuum at 1050C. This alloy is remelted in vacuum at 1100C with the Si and Al to give the final alloy. This alloy was placed in a fused silica tube with a 0.012 inch diameter hole in the bottomand melted at 1,100C. A gas pressure of8 psi is applied to the tube to force the molten metal through the hole, and the stream of molten alloy is directed into the nip of the rotating double rolls, held at room temperature, described by Chen and Miller in Rev. Sci. lnstrum. 41, 1237 (1970). The rolls are two inches in diameter and were rotating at 1500 rpm. The quenched metal was entirely amorphous as determined by x-ray diffraction measurements, was ductile to bending and exhibited tensile strengths to 350,000 psi. Alloys containing only Fe-P-C, such as Fe P C Fe P, C and Fe P C similarly quenched, are brittle and partially crystalline, as determined by x-ray diffraction. Further, the amorphous Fe P C Al Si, alloy exhibits the thermal manifestation of the glass transition, i.e. rapid increase in the specific heat, while amorphous Fe-P-C alloys do not.

EXAMPLE 2 An alloy of composition Ni Fe P B Al is melted at 1,020C and quenched to an amorphous metal in the manner of and following the procedure of Example 1. An alloy with improved thermal stability and high bending ductility, strength, and corrosion resistance is obtained. X-ray diffraction measurements are used to confirm its amorphous structure.

EXAMPLE 3 The molten alloy of Example 2 is quenched to the amorphous state using the Pond and Maddin teaching wherein the molten stream is directed through a 0.020 inch hole onto the surface of a copper hollow cylinder which is open at one end, has an inner diameter of six inches, is at room temperature and is rotating at 2500 rpm. An amorphous metal ribbon having the properties of that obtained in Example 2 was obtained,

EXAMPLES 4 17 Following the procedures of Example 1, the amorphous alloys set forth in Table l were obtained.

The alloy of composition Ni P B Si was obtained in the amorphous state by flash evaporation as follows: A fine powder, ,u. particles, of crystalline Ni P B- Si was slowly sprinkled onto a hot tungsten filament (-1,600C) in a vacuum of about 10 mm Hg. The vaporized alloy was condensed onto a nearby copper substrate kept at room temperature so that the amorphous state of the same composition was achieved.

EXAMPLES l9 24 Following the procedure of Example 18, the amorphous alloys set forth in Table II were obtained by flash EXAMPLE 25 A Pd Cu Si, alloy was melted in a fused silica tube which had been drawn to a point with a 0.008 inch hole at the tip and containing an argon atomosphere within a furnace held at 870C. The melt was held in the tube by its surface tension. The silica tube was rapidly lowered through the furnace so that the tip of the tube was held 0.1 inch above the surface of water contained in a vessel at room temperature and the melt was ejected into the water upon applying 6 psi of gas pressure to the tube. A continuous, smooth amorphous wire of round cross-section with a diameter of about 0.008 inch was obtained. The glassy (amorphous) nature of the wire product was confirmed by x-ray diffraction. The wire has an elastic limit of about 160,000 psi and a tensile strength of about 230,000 psi which is about one-fiftieth of the Youngs modulus for this glass, a value which approaches the theoretical strength of this material.

EXAMPLE 26 Pd-, Cu Si was melt spun to a wire of uniform cross section using the process and apparatus described by Kavesh in the above-noted US. application, Ser. No. 306,472, with an orifice diameter of 0.005 inch and C water as the quench medium to yield an amorphous product.

EXAMPLE 27 Following the procedure of Example 25, a Ni Feg P B ShAl alloy was melted at l000C and ejected from a 0.005 inch hole into brine held at C to produce a glassy wire whose amorphous character is confirmed by xray diffraction.

EXAMPLE 28 Following the procedure of Example 26, a

10 Fe P, C B,Si Al alloy was spun to a glassy wire using a 0.005 inch hole and -20C brine as the quench medium. The amorphous character of the wire is confirmed by x-ray diffraction.

EXAMPLE 29 Following the procedure of Example 26, a Ni40Pd4oP2n alloy was melted at 700C and melt spun through a 0.005 inch orifice into iced brine at 20C to give a glassy wire. the amorphous characterization is confirmed by x-ray diffraction.

We claim:

1. A metal alloy of the formula M,,Y,,Z which is at least 50 percent amorphous and wherein M is a metal selected from the group consisting essentially of iron, nickel, chromium, cobalt, or vanadium or a mixture thereof, Y is a metalloid selected from the-group consisting of phosphorus, carbon and boron or a mixture thereof, and Z isan element selected from the group consisting of aluminum, silicon, tin, antimony, germa' nium, indium, and beryllium and mixtures thereof, 19" and 0" are atomic percentages ranging from about 60 to 90, 10 to 30 and 0.1 to 15 respectively with the proviso that a plus b plus c equals. 100.

2. The amorphous metal alloy of claim 1 wherein a, b" and 0 range from 69 to 84.5, 15 to 25, and 0.5 to 6, respectively.

3. The amorphous metal alloy of claim 1 wherein up to about one-fourth of the metal M is replaced by elements commonly alloyed with iron or nickel.

4. As an article of manufacture, sheets,ribbons and powders of the amorphous metals having the compositions of claim 1.

5. As an article of manufacture, sheets, ribbons and powders of the amorphous metals having the compositions of claim 3.

6. As an article of manufacture, a metal wire comprising an alloy which is at least 50 percent amorphous and having a composition of the formula T X, wherein T is a transition metal or mixture of said transition met als and X is an element selected from the group consisting of aluminum, antimony, beryllium, boron, germanium, carbon, indium, phosphorus, silicon, tin, and mixtures thereof and wherein i andj are in atomic percentages and range from about 70 to about 87 and from about 13 to about 30 respectively.

7. The article of claim 6 wherein i ranges from about 74 to about 84 andj ranges from about 16 to about 26.

8. Amorphous metal wire of claim 6 wherein iron comprises at least 60 atomic percent of T.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3403996 *May 31, 1966Oct 1, 1968Matsushita Electric Ind Co LtdFerromagnetic material
US3406057 *Mar 25, 1966Oct 15, 1968Matsushita Electric Ind Co LtdFerromagnetic material
US3427154 *Sep 11, 1964Feb 11, 1969IbmAmorphous alloys and process therefor
US3433630 *Oct 13, 1966Mar 18, 1969Matsushita Electric Ind Co LtdMagnetic permeability material
US3461943 *Oct 17, 1966Aug 19, 1969United Aircraft CorpProcess for making filamentary materials
US3542542 *Apr 5, 1968Nov 24, 1970Matsushita Electric Ind Co LtdMagnetic permeability material
US3543831 *Jan 9, 1967Dec 1, 1970United Aircraft CorpElectrostatic coatings
US3658979 *Jun 2, 1969Apr 25, 1972Monsanto CoMethod for forming fibers and filaments directly from melts of low viscosities
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3940293 *Jan 27, 1975Feb 24, 1976Allied Chemical CorporationMethod of producing amorphous cutting blades
US3986867 *Jan 13, 1975Oct 19, 1976The Research Institute For Iron, Steel And Other Metals Of The Tohoku UniversityIron-chromium series amorphous alloys
US3986901 *Apr 30, 1975Oct 19, 1976International Business Machines CorporationControlled catalyst for manufacturing magnetic alloy particles having selective coercivity
US3989517 *Apr 28, 1975Nov 2, 1976Allied Chemical CorporationHigh strength, low density
US4007072 *Nov 18, 1974Feb 8, 1977Fuji Photo Film Co., Ltd.Ferromagnetic metal powder comprising lead and method for making the same
US4030892 *Mar 2, 1976Jun 21, 1977Allied Chemical CorporationFlexible electromagnetic shield comprising interlaced glassy alloy filaments
US4033795 *Jun 4, 1974Jul 5, 1977International Business Machines CorporationMethod for inducing uniaxial magnetic anisotropy in an amorphous ferromagnetic alloy
US4036638 *Nov 28, 1975Jul 19, 1977Allied Chemical CorporationSoft magnetic properties
US4038073 *Mar 1, 1976Jul 26, 1977Allied Chemical CorporationCobalt, iron, boron, carbon
US4050931 *Jul 27, 1976Sep 27, 1977Allied Chemical CorporationAmorphous metal alloys in the beryllium-titanium-zirconium system
US4052201 *Jun 26, 1975Oct 4, 1977Allied Chemical CorporationAmorphous alloys with improved resistance to embrittlement upon heat treatment
US4053331 *Jul 29, 1976Oct 11, 1977University Of PennsylvaniaMethod of making amorphous metallic alloys having enhanced magnetic properties by using tensile stress
US4053332 *Jul 29, 1976Oct 11, 1977University Of PennsylvaniaEnhancing magnetic properties of amorphous alloys by rolling
US4053333 *Jul 29, 1976Oct 11, 1977University Of PennsylvaniaEnhancing magnetic properties of amorphous alloys by annealing under stress
US4056411 *May 14, 1976Nov 1, 1977Ho Sou ChenCobalt-iron, heat treatment
US4059441 *Nov 11, 1976Nov 22, 1977Allied Chemical CorporationMetallic glasses with high crystallization temperatures and high hardness values
US4067732 *Jun 26, 1975Jan 10, 1978Allied Chemical CorporationAmorphous alloys which include iron group elements and boron
US4081298 *Sep 7, 1976Mar 28, 1978Allied Chemical CorporationHeat treatment of iron-nickel-phosphorus-boron glassy metal alloys
US4085396 *Sep 27, 1976Apr 18, 1978Bell Telephone Laboratories, IncorporatedElectric fuse
US4113478 *Aug 9, 1977Sep 12, 1978Allied Chemical CorporationZirconium alloys containing transition metal elements
US4115682 *Nov 24, 1976Sep 19, 1978Allied Chemical CorporationWelding of glassy metallic materials
US4116682 *Dec 27, 1976Sep 26, 1978Polk Donald EAmorphous metal alloys and products thereof
US4116687 *Aug 5, 1977Sep 26, 1978Allied Chemical CorporationGlassy superconducting metal alloys in the beryllium-niobium-zirconium system
US4116728 *Sep 2, 1976Sep 26, 1978General Electric CompanyTreatment of amorphous magnetic alloys to produce a wide range of magnetic properties
US4118222 *Jun 2, 1977Oct 3, 1978Allied Chemical CorporationGlassy hafnium-beryllium alloys
US4122240 *Mar 2, 1977Oct 24, 1978United Technologies CorporationSkin melting
US4126287 *Jun 9, 1977Nov 21, 1978Allied Chemical CorporationFlexible electromagnetic shield comprising interlaced glassy alloy filaments
US4126449 *Aug 9, 1977Nov 21, 1978Allied Chemical CorporationZirconium-titanium alloys containing transition metal elements
US4126494 *Oct 19, 1976Nov 21, 1978Kokusai Denshin Denwa Kabushiki KaishaMagnetic transfer record film
US4133679 *Jan 3, 1978Jan 9, 1979Allied Chemical CorporationIron-refractory metal-boron glassy alloys
US4133681 *Jan 3, 1978Jan 9, 1979Allied Chemical CorporationMolybdenum, tungsten
US4133682 *Jan 3, 1978Jan 9, 1979Allied Chemical CorporationMolybdenum, tungsten
US4135924 *Aug 9, 1977Jan 23, 1979Allied Chemical CorporationFilaments of zirconium-copper glassy alloys containing transition metal elements
US4137075 *May 25, 1977Jan 30, 1979Allied Chemical CorporationHeat resistance
US4140525 *Jan 3, 1978Feb 20, 1979Allied Chemical CorporationUltra-high strength glassy alloys
US4148669 *Apr 3, 1978Apr 10, 1979Allied Chemical CorporationZirconium-titanium alloys containing transition metal elements
US4148973 *Jun 5, 1978Apr 10, 1979Allied Chemical CorporationHomogeneous, ductile brazing foils
US4150981 *Aug 15, 1977Apr 24, 1979Allied Chemical CorporationAnd boron
US4152144 *Dec 29, 1976May 1, 1979Allied Chemical CorporationMetallic glasses having a combination of high permeability, low magnetostriction, low ac core loss and high thermal stability
US4152146 *Dec 29, 1976May 1, 1979Allied Chemical CorporationMolybdenum, boron, iron and impurities
US4152147 *Apr 10, 1978May 1, 1979Allied Chemical CorporationImproved thermal stability
US4152486 *Mar 10, 1977May 1, 1979Kokusai Denshin Denwa Kabushiki KaishaCurie temperature, alloy of dysprosium and iron
US4169744 *Jun 28, 1978Oct 2, 1979Western Gold And Platinum CompanyNickel-chromium-silicon alloy brazing foil
US4171992 *Apr 3, 1978Oct 23, 1979Allied Chemical CorporationPreparation of zirconium alloys containing transition metal elements
US4172718 *May 1, 1978Oct 30, 1979Siemens AktiengesellschaftTantalum and cobalt or nitrogen
US4174419 *Nov 8, 1978Nov 13, 1979Allied Chemical CorporationStabilized magnetic shields
US4186245 *Sep 28, 1978Jan 29, 1980Allied Chemical CorporationEnergy storage flywheel
US4188211 *Feb 9, 1978Feb 12, 1980Tdk Electronics Company, LimitedThermally stable amorphous magnetic alloy
US4189618 *Jul 31, 1978Feb 19, 1980Allied Chemical CorporationElectromagnetic shielding envelopes from wound glassy metal filaments
US4190438 *Sep 7, 1978Feb 26, 1980Sony CorporationRuthenium alloy having high permeability
US4197146 *Oct 24, 1978Apr 8, 1980General Electric CompanyMolded amorphous metal electrical magnetic components
US4201601 *Mar 8, 1979May 6, 1980Gte Sylvania IncorporatedCopper brazing alloy foils containing germanium
US4201837 *Nov 16, 1978May 6, 1980General Electric CompanyThin polymer-coated metal ribbons
US4202022 *Aug 14, 1978May 6, 1980Kokusai Denshin Denwa Kabushiki KaishaMagnetic transfer record film and apparatus for magneto-optically reading magnetic record patterns using the same
US4202089 *Jun 2, 1978May 13, 1980The Singer CompanySplat-cooled instrument flexure and method to fabricate same
US4210443 *Feb 27, 1978Jul 1, 1980Allied Chemical CorporationMolybdenum and/or tungsten
US4217135 *Nov 29, 1978Aug 12, 1980General Electric CompanyIron-boron-silicon ternary amorphous alloys
US4219355 *May 25, 1979Aug 26, 1980Allied Chemical CorporationIron-metalloid amorphous alloys for electromagnetic devices
US4221587 *Mar 23, 1979Sep 9, 1980Allied Chemical CorporationMethod for making metallic glass powder
US4221592 *Sep 2, 1977Sep 9, 1980Allied Chemical CorporationGlassy alloys which include iron group elements and boron
US4225339 *Dec 15, 1978Sep 30, 1980Tokyo Shibaura Denki Kabushiki KaishaAmorphous alloy of high magnetic permeability
US4226619 *May 4, 1979Oct 7, 1980Electric Power Research Institute, Inc.Iron-boron-carbon
US4229389 *Mar 16, 1979Oct 21, 1980Thompson Marine CorporationGas diffuser, aerator, or sparger apparatus
US4231816 *Dec 30, 1977Nov 4, 1980International Business Machines CorporationChromium, iron, cobalt
US4247398 *Oct 29, 1979Jan 27, 1981Tdk Electronics Co., Ltd.High gradient magnetic separation apparatus
US4248707 *Jan 17, 1980Feb 3, 1981Thompson Marine CorporationMagnetic chamber
US4249969 *Dec 10, 1979Feb 10, 1981Allied Chemical CorporationMethod of enhancing the magnetic properties of an Fea Bb Sic d amorphous alloy
US4256039 *Jan 2, 1979Mar 17, 1981Allied Chemical CorporationArmor-piercing projectile
US4258756 *Aug 27, 1979Mar 31, 1981Allied Chemical CorporationComposite shell
US4260007 *Mar 14, 1979Apr 7, 1981Allied Chemical CorporationMetal extrusion
US4260416 *Sep 4, 1979Apr 7, 1981Allied Chemical CorporationAmorphous metal alloy for structural reinforcement
US4265665 *Oct 1, 1979May 5, 1981Allied Chemical CorporationFoundry molds containing glassy metal alloy filaments
US4268325 *Jan 22, 1979May 19, 1981Allied Chemical CorporationAnnealing by heat treatment in magnetic field
US4283225 *Nov 13, 1978Aug 11, 1981Allied Chemical CorporationJoints
US4290808 *Mar 23, 1979Sep 22, 1981Allied Chemical CorporationMetallic glass powders from glassy alloys
US4298409 *Mar 25, 1980Nov 3, 1981Allied Chemical CorporationMethod for making iron-metalloid amorphous alloys for electromagnetic devices
US4298862 *Apr 23, 1979Nov 3, 1981Allied Chemical CorporationAmorphous antipilferage marker
US4300950 *May 4, 1979Nov 17, 1981General Electric CompanyAmorphous metal alloys and ribbons thereof
US4302515 *Aug 20, 1979Nov 24, 1981Allied CorporationDuctile foil
US4309214 *Aug 27, 1979Jan 5, 1982L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges ClaudeManufacture of metal powder
US4314661 *Apr 9, 1981Feb 9, 1982Allied CorporationHomogeneous, ductile brazing foils
US4316572 *Jun 23, 1980Feb 23, 1982Allied CorporationHomogeneous, ductile brazing foils
US4318738 *Oct 3, 1979Mar 9, 1982Shin-Gijutsu Kaihatsu JigyodanAmorphous carbon alloys and articles manufactured from said alloys
US4321090 *Mar 6, 1980Mar 23, 1982Allied CorporationMagnetic amorphous metal alloys
US4331497 *Dec 1, 1980May 25, 1982Allied CorporationComposite shell
US4338131 *Feb 19, 1980Jul 6, 1982Allied CorporationNickel-boron binary amorphous alloys
US4339270 *Apr 14, 1980Jul 13, 1982Toyo Soda Manufacturing Co. Ltd.Corrosion resistant amorphous noble metal-base alloys
US4341845 *Dec 22, 1978Jul 27, 1982General Electric CompanyHelical metallic ribbon for continuous edge winding applications
US4353737 *Apr 17, 1981Oct 12, 1982Allied CorporationAnnealing, embrittlement, comminution
US4359352 *Nov 19, 1979Nov 16, 1982Marko Materials, Inc.Nickel base superalloys which contain boron and have been processed by a rapid solidification process
US4379720 *Mar 15, 1982Apr 12, 1983Marko Materials, Inc.Nickel-aluminum-boron powders prepared by a rapid solidification process
US4381943 *Jul 20, 1981May 3, 1983Allied CorporationAlloy of boron, iron, nickel and cobalt
US4385932 *Jun 4, 1981May 31, 1983Tokyo Shibaura Denki Kabushiki KaishaIron, nickel, silicon, boron
US4385944 *May 29, 1980May 31, 1983Allied CorporationMagnetic implements from glassy alloys
US4389262 *Dec 31, 1980Jun 21, 1983Allied CorporationAmorphous alloys of nickel, aluminum and boron
US4392072 *Sep 13, 1978Jul 5, 1983General Electric CompanyDynamoelectric machine stator having articulated amorphous metal components
US4406700 *Jul 13, 1981Sep 27, 1983Allied CorporationPowder produced by embrittling of metallic glassy alloy by hydrogen charging
US4409041 *Jul 29, 1981Oct 11, 1983Allied CorporationIron-boron-silicon
US4409296 *Oct 22, 1980Oct 11, 1983Allegheny Ludlum Steel CorporationRapidly cast alloy strip having dissimilar portions
US4439236 *Apr 26, 1982Mar 27, 1984Allied CorporationComplex boride particle containing alloys
US4439253 *Mar 4, 1982Mar 27, 1984Allied CorporationCobalt rich manganese containing near-zero magnetostrictive metallic glasses having high saturation induction
US4448618 *Feb 28, 1983May 15, 1984Allied CorporationPalladium-silicon-nickel glassy alloys
US4450206 *May 27, 1982May 22, 1984Allegheny Ludlum Steel CorporationAmorphous metals and articles made thereof
US4464208 *Dec 30, 1982Aug 7, 1984Tokyo Shibaura Denki Kabushiki KaishaAmorphous alloy for magnetic head
US4469536 *Nov 10, 1982Sep 4, 1984The United States Of America As Represented By The Secretary Of The NavyAlloys and method of making
US4470553 *Apr 23, 1981Sep 11, 1984Allied CorporationInline winder
US4473413 *Mar 16, 1983Sep 25, 1984Allied CorporationIron-boron-silicon-carbon-chromium; for high frequency applications
US4473417 *Aug 6, 1982Sep 25, 1984Tokyo Shibaura Denki Kabushiki KaishaAmorphous alloy for magnetic core material
US4484184 *Aug 13, 1981Nov 20, 1984Allied CorporationFerromagnetic material
US4489136 *Apr 26, 1983Dec 18, 1984Allied CorporationHomogeneous low melting point copper based alloys
US4495487 *Oct 27, 1982Jan 22, 1985Allied CorporationSignal retention by a ferromagnetic strip after flexing or bending
US4495691 *Mar 29, 1982Jan 29, 1985Tsuyoshi MasumotoMelt spinning iron base alloys
US4503085 *Feb 7, 1983Mar 5, 1985Allied CorporationAmorphous metal powder for coating substrates
US4508257 *Mar 7, 1984Apr 2, 1985Allied CorporationPalladium, silicon
US4510490 *Jun 3, 1982Apr 9, 1985Allied CorporationCoded surveillance system having magnetomechanical marker
US4517017 *Feb 8, 1982May 14, 1985Tokyo Shibaura Denki Kabushiki KaishaCobalt, iron, nickel base alloys
US4520335 *Apr 6, 1983May 28, 1985Westinghouse Electric Corp.Transformer with ferromagnetic circuits of unequal saturation inductions
US4523626 *Apr 9, 1984Jun 18, 1985Tsuyoshi MasumotoAmorphous metal filaments and process for producing the same
US4523950 *Nov 9, 1981Jun 18, 1985Allied CorporationBoron containing rapid solidification alloy and method of making the same
US4525223 *Apr 9, 1984Jun 25, 1985Noboru TsuyaSilicon, non-metallics, semi-metallics, metallics, all melted and rapidly cooled
US4525314 *Nov 8, 1982Jun 25, 1985Torobin Leonard BProducing metal and metal glass microfilaments
US4527614 *Apr 9, 1984Jul 9, 1985Unitika Ltd.Amorphous Co-based metal filaments and process for production of the same
US4533389 *Dec 29, 1980Aug 6, 1985Allied CorporationBoron containing rapid solidification alloy and method of making the same
US4536361 *Nov 16, 1982Aug 20, 1985Torobin Leonard BMethod for producing plastic microfilaments
US4537517 *Oct 18, 1983Aug 27, 1985Tokyo Shibaura Denki Kabushiki KaishaNickel-iron or nickel-cobalt type alloy
US4543135 *Nov 15, 1982Sep 24, 1985Allied CorporationNickel high-chromium base brazing filler metal for high temperature applications
US4553136 *Feb 4, 1983Nov 12, 1985Allied CorporationAmorphous antipilferage marker
US4557769 *Jul 16, 1984Dec 10, 1985Alps Electric Co., Ltd.Soft magnetic material
US4560454 *Feb 26, 1985Dec 24, 1985The Standard Oil Company (Ohio)Electrolysis of halide-containing solutions with platinum based amorphous metal alloy anodes
US4566323 *Jul 29, 1983Jan 28, 1986Aisin Seiki Kabushiki KaishaResistance wire, superconductivity, amorphous, alloy
US4573630 *Aug 27, 1984Mar 4, 1986Allied CorporationHomogeneous low melting point copper based alloys
US4576653 *Apr 3, 1985Mar 18, 1986Allied CorporationMethod of making complex boride particle containing alloys
US4588452 *Jun 18, 1984May 13, 1986Allied CorporationAmorphous alloys for electromagnetic devices
US4606977 *Oct 22, 1984Aug 19, 1986Allied CorporationFlame or plasma spraying group 8 metal boride coatinh
US4609442 *Jun 24, 1985Sep 2, 1986The Standard Oil CompanyElectrolysis of halide-containing solutions with amorphous metal alloys
US4612161 *Oct 20, 1983Sep 16, 1986The United States Of America As Represented By The United States Department Of EnergyFabrication of metallic glass structures
US4614221 *Sep 29, 1982Sep 30, 1986Unitika Ltd.Method of manufacturing thin metal wire
US4617983 *May 16, 1985Oct 21, 1986Unitika Ltd.Method and apparatus for continuously manufacturing metal filaments
US4634462 *Jan 9, 1985Jan 6, 1987Allied CorporationPermeablility changes
US4643058 *May 10, 1984Feb 17, 1987Allied CorporationFloating gang rotary slitting device and method
US4650130 *Jan 4, 1982Mar 17, 1987Allied CorporationRapidly solidified powder production system
US4655079 *Nov 21, 1984Apr 7, 1987Aisin Seiki Kabushiki KaishaUsing amorphous zirconium, ruthenium, and rhodium alloy
US4655857 *Mar 8, 1983Apr 7, 1987Tsuyoshi MasumotoNi-Cr type alloy material
US4696731 *Dec 16, 1986Sep 29, 1987The Standard Oil CompanyMixed metal oxide coating over amorphous metal alloy coating; fusion
US4702302 *Aug 20, 1986Oct 27, 1987Sumitomo Electric Industries Ltd.Method of making thin alloy wire
US4702813 *Dec 16, 1986Oct 27, 1987The Standard Oil CompanyApplying one alloy coating, then different second alloy coating
US4705610 *May 27, 1986Nov 10, 1987The Standard Oil CompanyAnodes containing iridium based amorphous metal alloys and use thereof as halogen electrodes
US4727202 *May 18, 1987Feb 23, 1988Lonza Ltd.Oxidative or reductive treatment of amorphous alloys
US4735789 *Jul 25, 1985Apr 5, 1988Lonza Ltd.Process for the production of catalytically-active metallic glasses
US4735864 *Apr 2, 1987Apr 5, 1988Tsuyoshi Masumoto and Unitika, LimitedIron, silicon, boron
US4743313 *Nov 12, 1985May 10, 1988Alps Electric Co., Ltd.Amorphous alloy for use in magnetic heads
US4745037 *Nov 17, 1986May 17, 1988Allied CorporationGlassy aloys for brazing stainless steels
US4745806 *Jan 24, 1986May 24, 1988Aisin Seiki Kabushiki KaishaSuperconductive alloys
US4746584 *Jun 24, 1985May 24, 1988The Standard Oil CompanyNovel amorphous metal alloys as electrodes for hydrogen formation and oxidation
US4750951 *Feb 11, 1987Jun 14, 1988Alps Electric Co., Ltd.Wear and corrosion resistance
US4760333 *Nov 6, 1985Jul 26, 1988Kanto Seiki Co., Ltd.Crossed coil meter having concentrically wound magnetic shield
US4781771 *Dec 30, 1986Nov 1, 1988Unitika Ltd.Amorphous Co-based metal filaments and process for production of the same
US4781803 *Jun 16, 1986Nov 1, 1988The Standard Oil CompanyElectrolytic processes employing platinum based amorphous metal alloy oxygen anodes
US4823113 *Mar 14, 1988Apr 18, 1989Allied-Signal Inc.Glassy alloy identification marker
US4834814 *Mar 7, 1988May 30, 1989Allied-Signal Inc.Metallic glasses having a combination of high permeability, low coercivity, low AC core loss, low exciting power and high thermal stability
US4834816 *Dec 4, 1987May 30, 1989Allied-Signal Inc.Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability
US4839487 *Dec 3, 1986Jun 13, 1989Mitsubishi Denki Kabushiki KaishaWire electrode for wire-cut electrical discharge machining
US4889568 *Jul 28, 1983Dec 26, 1989Allied-Signal Inc.Annealing iron, boron, silicon alloy in absence of magnetic field
US4916109 *Jul 13, 1988Apr 10, 1990Lonza Ltd.Palladium zirconium oxide
US4956743 *Jan 19, 1990Sep 11, 1990Allied-Signal Inc.Ground fault interrupters for glassy metal alloys
US4968363 *Nov 22, 1988Nov 6, 1990Mitsui Engineering & Shipbuilding Co., Ltd.Method of preventing corrosion of a material against hydrochloric acid
US4978513 *Jan 4, 1989Dec 18, 1990Lonza Ltd.Catalyst for the oxidation of carbon compounds
US4989989 *Aug 31, 1989Feb 5, 1991Westinghouse Electric Corp.Hydraulic sensor for quench detection and location in superconductors
US5011553 *Jul 14, 1989Apr 30, 1991Allied-Signal, Inc.Iron-rich metallic glasses having high saturation induction and superior soft ferromagnetic properties
US5035755 *Dec 11, 1990Jul 30, 1991Allied-Signal Inc.Amorphous metal alloys having enhanced AC magnetic properties at elevated temperatures
US5041175 *Oct 5, 1990Aug 20, 1991Yoshida Kogyo K.K.Amorphous aluminum alloys
US5055144 *Jun 26, 1990Oct 8, 1991Allied-Signal Inc.Annealing amorphous alloy, transforming to different resistivity
US5060478 *Aug 31, 1989Oct 29, 1991Research Development Corporation Of JapanMagnetical working amorphous substance
US5076865 *Oct 13, 1989Dec 31, 1991Yoshida Kogyo K. K.High corrosion resistance, toughness; containing valve metals, zirconium and titanium
US5110378 *Dec 6, 1990May 5, 1992Allied-Signal Inc.Metallic glasses having a combination of high permeability, low coercivity, low ac core loss, low exciting power and high thermal stability
US5158229 *Jan 24, 1992Oct 27, 1992Allied-Signal Inc.Low temperature, high strength, nickel, base brazing alloys
US5200002 *Jun 5, 1980Apr 6, 1993Vacuumschmelze GmbhOf cobalt, manganese, silicon, boron and other metals; use for magnetic screens, sound heads and magnetic cores
US5240066 *Sep 26, 1991Aug 31, 1993Technalum Research, Inc.Method of casting amorphous and microcrystalline microwires
US5277977 *Dec 29, 1989Jan 11, 1994Tdk CorporationFerromagnetic stabilized ultrafine spherical hexagonal crystalline Fe2
US5278377 *Nov 27, 1991Jan 11, 1994Minnesota Mining And Manufacturing CompanyElectromagnetic radiation susceptor material employing ferromagnetic amorphous alloy particles
US5279349 *Oct 13, 1992Jan 18, 1994Honda Giken Kogyo Kabushiki KaishaProcess for casting amorphous alloy member
US5370749 *Jul 30, 1992Dec 6, 1994Allegheny Ludlum CorporationAmorphous metal alloy strip
US5443664 *Nov 8, 1989Aug 22, 1995Hitachi Metals, Ltd.Surge current-suppressing circuit and magnetic device therein
US5456770 *Aug 8, 1994Oct 10, 1995Nippon Steel CorporationContaining iron, silicon, boron, zinc
US5518518 *Oct 14, 1994May 21, 1996Fmc CorporationAmorphous metal alloy and method of producing same
US5583734 *Nov 10, 1994Dec 10, 1996Raychem CorporationSurge arrester with overvoltage sensitive grounding switch
US5683822 *Apr 6, 1995Nov 4, 1997Nippon Steel CorporationLiquid-phase diffusion bonding alloy foils for joining heat-resistant metals in oxidizing atmospheres
US5759300 *Mar 29, 1995Jun 2, 1998Nippon Steel CorporationLiquid-phase diffusion bonding alloy foils for joining heat-resistant metals in oxidizing atmospheres
US5961746 *Aug 15, 1997Oct 5, 1999Read-Rite CorporationCorrosion resistant amorphous magnetic alloys
US6053989 *Feb 12, 1998Apr 25, 2000Fmc CorporationAlloys of iron, chromium, vanadium, phosphorous, silicon, carbon and metals
US6103396 *Aug 29, 1997Aug 15, 2000Alliedsignal Inc.An amorphous metal strips having a large thickness produced by a melt spin process wherein a stream of molten metal alloy is quenched and solidified on the peripheral surface of a rotating annular chill roll
US6277212Sep 27, 1982Aug 21, 2001Ati Properties, Inc.Amorphous metal alloy strip and method of making such strip
US6296948Feb 17, 1981Oct 2, 2001Ati Properties, Inc.Alloy of iron, boron and silicon for heat resistance
US6432226Apr 12, 1999Aug 13, 2002Alliedsignal Inc.A magnetic alloy that is at least 70% glassy, having the formula cobalt, nickel, iron, boron, silicon, carbon and a metal selected from chromium, molybdenum, manganese, niobium in a specific atom percent
US6471789May 18, 1995Oct 29, 2002Ati PropertiesAmorphous metal alloy strip
US6475303Aug 8, 2000Nov 5, 2002Honeywell International Inc.Magnetic glassy alloys for electronic article surveillance
US6481088 *Jul 9, 1998Nov 19, 2002Akihisa InoueGolf club manufacturing method
US6585033 *Feb 19, 2002Jul 1, 2003Fukuda Metal Foil & Powder Co., Ltd.Process for producing vanadium alloy foil
US6749695Feb 8, 2002Jun 15, 2004Ronald J. MartisHeat-treated to induce low magnetic loss; up to 20% fe may be replaced by co, and up to 3% by ni, mn, v, ti or mo; the balance comprising b, si or c
US6869566Mar 5, 2003Mar 22, 2005The United States Of America As Represented By The Secretary Of The Air ForceMethod of fabricating metallic glasses in bulk forms
US6930581Feb 8, 2002Aug 16, 2005Metglas, Inc.Current transformer having an amorphous fe-based core
US7052561 *Aug 12, 2003May 30, 2006Ut-Battelle, LlcBulk amorphous steels based on Fe alloys
US7589266Aug 21, 2006Sep 15, 2009Zuli Holdings, Ltd.Musical instrument string
US7670406Mar 15, 2007Mar 2, 2010Belashchenko Vladimir EDeposition system, method and materials for composite coatings
US7771545Apr 12, 2007Aug 10, 2010General Electric CompanyCobalt, iron, chromium, manganese, Molybdenum, Vanadium, Boron, Silicon, Phophorus; tensile strength greater than 3500 MPa; electrical resistivity greater than 145 .mu..OMEGA.-cm.; anode wire
US7785428Jan 5, 2004Aug 31, 2010Battelle Energy Alliance, LlcMethod of forming a hardened surface on a substrate
US8049088Jul 1, 2009Nov 1, 2011Zuli Holdings, Ltd.Musical instrument string
US8057530Jun 29, 2007Nov 15, 2011Tyco Healthcare Group LpMedical devices with amorphous metals, and methods therefor
US8097095 *Jan 5, 2004Jan 17, 2012Battelle Energy Alliance, LlcHardfacing material
US20070175545 *Feb 1, 2007Aug 2, 2007Nec Tokin CorporationAmorphous soft magnetic alloy and inductance component using the same
US20120076946 *Nov 7, 2011Mar 29, 2012Lawrence Livermore National Security, LlcAmorphous Metal Formulations and Structured Coatings for Corrosion and Wear Resistance
US20120276404 *Aug 25, 2011Nov 1, 2012Hon Hai Precision Industry Co., Ltd.Coated article and method for making the same
USRE29239 *Sep 17, 1975May 31, 1977Whyco Chromium Company Inc.Ternary alloys
USRE29989 *Mar 15, 1977May 8, 1979Allied Chemical CorporationCutting blades made of or coated with an amorphous metal
USRE30080 *Aug 11, 1977Aug 21, 1979Allied Chemical CorporationTitanium-beryllium base amorphous alloys
USRE30106 *Feb 21, 1978Oct 2, 1979Allied Chemical CorporationMethod of producing amorphous cutting blades
USRE32427 *Jun 3, 1985May 26, 1987 Amorphous antipilferage marker
USRE32428 *Jun 3, 1985May 26, 1987Allied CorporationAmorphous antipilferage marker
USRE35042 *Apr 22, 1993Sep 26, 1995Allied CorporationAmorphous antipilferage marker
DE2839626A1 *Sep 12, 1978Mar 22, 1979Sony CorpAmorphe magnetische legierung
DE3010506A1 *Mar 19, 1980Sep 25, 1980Allied ChemMetallglaspulver und verfahren zu dessen herstellung
DE3011152A1 *Mar 22, 1980Oct 2, 1980Allied ChemBorhaltige legierungen, verfahren zu deren herstellung und deren verwendung
DE3106607A1 *Feb 23, 1981Sep 9, 1982Kammerer F GmbhPlattierverfahren
DE3422281A1 *Jun 15, 1984Dec 20, 1984Allied CorpProcess for manufacturing mouldings from magnetic metal alloys, and mouldings thus produced
DE3645282C2 *Dec 2, 1986Feb 8, 1996Gen ElectricTransformer with amorphous ferromagnetic laminated core
DE3690625C2 *Dec 2, 1986Jan 20, 1994Gen ElectricVerfahren zum Herstellen einer Baueinheit aus einem magnetischen Kern aus amorphem Metall und einer Spulenstruktur für einen elektrischen Transformator und elektrischer Transformator
DE3704499A1 *Feb 13, 1987Aug 20, 1987Gen ElectricTransformatorkern
DE3841748A1 *Dec 12, 1988Jul 27, 1989Alps Electric Co LtdLegierung mit hochgesaettigter magnetischer flussdichte
DE102011001783A1 *Apr 4, 2011Oct 4, 2012Vacuumschmelze Gmbh & Co. KgSpring useful for mechanical clockwork comprises amorphous alloy comprising e.g. nickel cobalt iron chromium boron silicon carbon phosphorous molybdenum niobium vanadium tantalum tungsten compound
DE102011001784A1 *Apr 4, 2011Oct 4, 2012Vacuumschmelze Gmbh & Co. KgPreparing a spring e.g. lift spring and/or mainspring for a mechanical clockwork, comprises melting an alloy, forming an amorphous tape from the melted alloy by a rapid solidification method, and processing a surface of the amorphous tape
EP0002909A1 *Dec 14, 1978Jul 11, 1979Allied CorporationAmorphous alloys and filaments thereof
EP0007062A1 *Jul 4, 1979Jan 23, 1980Allied CorporationPreparation of phosphorus-containing metallic glass-forming alloy melts
EP0010866A1 *Sep 28, 1979May 14, 1980Allied CorporationHomogeneous brazing foils of copper based metallic glasses
EP0011703A1 *Oct 16, 1979Jun 11, 1980Allied CorporationMagnetic composite structure and method for making said structure
EP0014335A1 *Jan 15, 1980Aug 20, 1980Allied CorporationHomogeneous ductile brazing foils
EP0016916A1 *Jan 28, 1980Oct 15, 1980Allied CorporationHomogeneous ductile brazing foils
EP0017723A1 *Feb 15, 1980Oct 29, 1980Allied CorporationMethod and apparatus for making metallic glass powder
EP0018507A1 *Apr 1, 1980Nov 12, 1980Allied CorporationBeryllium-containing iron-boron glassy magnetic alloys and devices utilizing same
EP0019682A1 *Jan 22, 1980Dec 10, 1980Allied CorporationMethod for making metallic glass powder
EP0020937A1 *Apr 26, 1980Jan 7, 1981Allied CorporationMethod of enhancing the magnetic properties of amorphous metal alloys
EP0026863A1 *Sep 19, 1980Apr 15, 1981Allied CorporationCorrosion resistant glassy metal alloys
EP0027502A1 *Jul 22, 1980Apr 29, 1981Allied CorporationComposite shell formed of glassy metal alloy strips
EP0027515A1 *Aug 16, 1980Apr 29, 1981Allied CorporationAmorphous metal useful as structural reinforcement
EP0035644A1 *Feb 3, 1981Sep 16, 1981Allied CorporationMagnetic amorphous metal alloys
EP0038584A1 *Mar 30, 1981Oct 28, 1981BBC Aktiengesellschaft Brown, Boveri & Cie.Multi-layered-solder and method of producing such solder
EP0039169A2 *Apr 14, 1981Nov 4, 1981Tsuyoshi MasumotoAmorphous metal filaments and process for producing the same
EP0050479A1 *Oct 15, 1981Apr 28, 1982Unitika Ltd.Amorphous co-based metal filaments and process for the production of the same
EP0055327A1 *Sep 23, 1981Jul 7, 1982Allied CorporationAmorphous metal alloys having enhanced AC magnetic properties
EP0055371A1 *Oct 27, 1981Jul 7, 1982Kabushiki Kaisha ToshibaNeutron absorber, neutron absorber assembly utilizing the same, and other uses thereof
EP0055403A1 *Dec 7, 1981Jul 7, 1982Allied CorporationAmorphous alloys of nickel, aluminum and boron
EP0056141A1 *Dec 21, 1981Jul 21, 1982Allied CorporationHomogeneous ductile nickel-palladium based brazing foils
EP0069406A2Mar 21, 1980Jan 12, 1983Allied CorporationMethod of making shaped articles from metallic glass bodies
EP0076918A1 *Aug 28, 1982Apr 20, 1983Allied CorporationAmorphous magnetic core and process for manufacturing to improve efficiency
EP0078401A1 *Oct 11, 1982May 11, 1983Allied CorporationAmorphous antipilferage marker
EP0086973A2 *Jan 25, 1983Aug 31, 1983Allied CorporationTuned vibration detector
EP0092091A2Apr 2, 1983Oct 26, 1983Allied CorporationApparatus for the production of magnetic powder
EP0093281A2 *Apr 11, 1983Nov 9, 1983Identitech CorporationSurveillance system having magnetomechanical marker
EP0096182A2 *Apr 9, 1983Dec 21, 1983Identitech CorporationCoded surveillance system having magnetomechanical marker
EP0100919A1 *Jul 16, 1983Feb 22, 1984Allied CorporationLow temperature, high strength nickel based brazing alloys
EP0103770A1 *Aug 23, 1983Mar 28, 1984Allied CorporationHomogeneous low melting point copper based alloys
EP0103805A1 *Sep 6, 1983Mar 28, 1984Allied CorporationHomogeneous low melting point copper based alloys
EP0121649A1 *Jan 13, 1984Oct 17, 1984Allied CorporationAmorphous antipilferage marker
EP0166864A1 *Mar 18, 1985Jan 8, 1986Allied CorporationFloating gang rotary slitting device
EP0170909A1 *Jul 9, 1985Feb 12, 1986Atlas Fahrzeugtechnik GmbHPiezoceramic valve plate for a low pressure injection valve and method for making it
EP0191107A1 *Jul 26, 1985Aug 20, 1986Research Development Corporation of JapanAmorphous material which operates magnetically
EP0745698A1 *Nov 23, 1995Dec 4, 1996Samsung Heavy Industries Co., Ltd.Corrosion and wear resistant iron alloy and method for preparing corrosion and wear resistant members using the same
EP0899353A2 *Aug 14, 1998Mar 3, 1999Alps Electric Co., Ltd.Sinter and casting comprising Fe-based high-hardness glassy alloy
WO1979000674A1 *Feb 1, 1979Sep 20, 1979Arakawa SAmorphous carbon alloys and articles manufactured therefrom
WO1980002123A1 *Mar 10, 1980Oct 16, 1980United Technologies CorpWire with rapidly quenched structure
WO1998027788A1 *Dec 19, 1996Jun 25, 1998Advanced Metal Technologies LtAmorphous metallic alloy electrical heater system
WO2003044754A1Nov 12, 2002May 30, 2003Honeywell Int IncElectronic article surveillance markers for recorded media
WO2003067615A1 *Feb 3, 2003Aug 14, 2003Honeywell Int IncCurrent transformer having an amorphous fe-based core
WO2004112862A1 *Jun 28, 2004Dec 29, 2004Dommann AlexProsthesis and method for the production thereof
Classifications
U.S. Classification148/403, 420/445, 420/435, 164/423, 420/441, 252/519.1, 374/176, 420/588, 164/480, 252/519.14, 164/463, 420/424, 164/462, 420/28, 420/14, 420/580
International ClassificationC22C30/00, C22C5/04, C22C45/00, C22C1/00, C22C5/06, C22C28/00, H01F1/12, C22C27/00, H01F1/147, C22C9/00, C22C27/04, C22C16/00, C22C14/00, H05K9/00, C22C19/00, H01C3/00, C22C45/04, H01F1/153, C22C5/02, C22C1/02, C22C27/06, C22C45/02, B22D11/00, C22C27/02, C22C5/00, C22C22/00
Cooperative ClassificationH05K9/009, H01C3/005, C22C45/00, C22C19/00, C22C27/025, C22C27/06, C22C45/02, H01F1/15391, B22D11/005
European ClassificationC22C27/06, C22C27/02B, B22D11/00B, C22C45/00, C22C19/00, C22C45/02, H01C3/00B, H05K9/00M4F, H01F1/153T
Legal Events
DateCodeEventDescription
Dec 9, 1986RFReissue application filed
Effective date: 19861023