GB1572284A - Amorphous metal alloys - Google Patents
Amorphous metal alloys Download PDFInfo
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- GB1572284A GB1572284A GB3622877A GB3622877A GB1572284A GB 1572284 A GB1572284 A GB 1572284A GB 3622877 A GB3622877 A GB 3622877A GB 3622877 A GB3622877 A GB 3622877A GB 1572284 A GB1572284 A GB 1572284A
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 78
- 239000000956 alloy Substances 0.000 claims description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 28
- 229910052804 chromium Inorganic materials 0.000 claims description 28
- 239000011651 chromium Substances 0.000 claims description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052752 metalloid Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002738 metalloids Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/008—Amorphous alloys with Fe, Co or Ni as the major constituent
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
Description
(54) AMORPHOUS METAL ALLOYS
(71) We, ALLIED CHEMICAL CORPORATION, a Corporation organized and existing under the laws of the State of New York, United States of America of Columbia
Road and Park Avenue, Morris County, New Jersey 07960, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The invention relates to amorphous metal alloy compositions, and, in particular, to amorphous alloys containing iron, nickel, cobalt and/or chromium having improved resistance to embrittlement upon heat treatment.
Investigations have demonstrated that it is possible to obtain solid amorphous metals for certain alloy compositions. An amorphous substance generally characterizes a noncrystalline or glassy substance, that is, a substance substantially lacking any long range order. In distinguishing an amorphous substance from a crystalline substance, X-ray diffraction measurements are generally suitably employed. Additionally, transmission electron micrography and electron diffraction can be used to distinguish between the amorphous and the crystalline state.
An amorphous metal produces an X-ray diffraction profile in which intensity varies slowly with diffraction angle. Such a profile is qualitatively similar to the diffraction profile of a liquid or ordinary window glass. On the other hand, a crystalline metal produces a diffraction profile in which intensity varies rapidly with diffraction angle.
These amorphous metals exist in a metastable state. Upon heating to a sufficiently high temperature, they crystallize with evolution of a heat of crystallization, and the X-ray diffraction profile changes from one having glassy or amorphous characteristics to one having crystalline characteristics.
It is possible to produce a metal which is totally amorphous or which comprises a twophase mixture of the amorphous and crystalline state. The term "amorphous metal", as employed herein, refers to a metal which is at least 50% amorphous, and preferably 80% amorphous, but which may have some fraction of the material present as included crystallites.
Proper processing will produce a metal alloy in the amorphous state. One typical procedure is to cause molten alloy to be spread thinly in contact with a solid metal substrate such as copper or aluminum so that the molten alloy loses its heat to the substrate. When the molten alloy is spread to a thickness at about 0.002 inch, cooling rates of the order of 106"C/sec are achieved. See, for example, R. C. Ruhl, Vol. 1, Materials Science and
Engineering, pp. 313-319 (1967), which discusses the dependence of cooling rates upon the conditions of processing the molten alloys. Any process which provides a suitable high cooling rate, as of the order of 105 to 1060C/sec, can be used. Illustrative examples of procedures which can be used to make the amorphous metals are the rotating double roll procedure described by H. S. Chen and C. E. Miller in Vol. 41, Review of Scientific
Instruments, pp. 1237-1238 (1970) and the rotating cylinder technique described by R.
Pond, Jr. and R. Maddin in Vol. 245, Transactions of the Metallurgical Society, AIME, pp.
2475-2476 (1969).
Novel amorphous metal alloys have been disclosed and claimed by H. S. Chen and D. E.
Polk in U.S. Patent 3,856,513, issue December 24, 1974. These amorphous alloys have the formula MaYbZc, where M is at least one metal selected from the group consisting of iron, nickel, cobalt, chromium and vanadium, Y is at least one element selected from the group consisting of phosphorus, boron and carbon, Z is at least one element selected from the group consisting of aluminum, antimony, beryllium, germanium, indium, tin and silicon "a" ranges from about 60 to 90 atom percent, "b" ranges from about 10 to 30 atom percent and "c" ranges from about 0.1 to 15 atom percent. These alloys have been found suitable for a wide variety of applications, including ribbon, sheet, wire or powder. Amorphous alloys are also disclosed and claimed having the formula TiXj, where T is at least one transition metal,
X is at least one element selected from the group consisting of aluminum, antimony, beryllium,xoron, germanium, carbon, indium, phosphorus, silicon and tin, "i" ranges from about 70 to 87 atom percent and "j" ranges from about 13 to 30 atom percent. These alloys have been found suitable for wire applications.
Ductility is generally desirable either to render mechanical applications possible or to ease the handling and processing of the product. It is known that amorphous metal alloys tend to lose ductility in bending upon heating to temperatures near which the onset of crystallization occurs (crystallization temperature). Often, prolonged heating at lower temperatures is sufficient to induce embrittlement. Many of the amorphous alloys containing iron, nickel, cobalt and/or chromium known in the art, which include phosphorus as an aid to glass formation, tend to embrittle upon heating in the temperature range of about 200" to 350"C. While many applications involving these amorphous alloys would not require such heat treatment, there are specific instances where such heating would be necessary and where it would be desirable to utilize these alloys, many of which are relatively inexpensive compositions.
The thermal stability of an amorphous metal alloy is an important property in certain applications. Thermal stability is characterized by the time-temperature transformation behavior of an alloy, and may be determined in part by DTA (differential thermal analysis).
As considered here, relative thermal stability is also indicated by the retention of ductility in bending after thermal treatment. Amorphous metal alloys with similar crystallization behavior as observed by DTA may exhibit different embrittlement behavior upon exposure to the same heat treatment cycle. By DTA measurement, crystallization temperatures, Tc, can be accurately determined by slowly heating an amorphous metal alloy (at 20 to 50 C/min) and noting whether excess heat is evolved over a limited temperature range (crystallization temperature) or whether excess heat is absorbed over a particular temperature range (glass transition temperature). In general, the glass transition temperature Tg is near the lowest, or first, crystallization temperature, Tcl, and, as is conventional, is the temperature at which the viscosity ranges from 10 i3 to 10 poise.
Most amorphous metal alloy compositions containing iron, nickel, cobalt and/or chromium which include phosphorus, among other metalloids, evidence ultimate tensile strengths of 265,000 to 350,000 psi and crystallization temperatures of 400" to 4600C. For example, an amorphous metal alloy having the composition Fe76P16C4Si2Al2 (the subscripts are in atom percent) has an ultimate tensile strength of about 310,000 psi and a crystallization temperature of about 460"C; an amorphous metal alloy having the composition Fe30Ni30Co20Pl3B5Si2 has an ultimate tensile strength of about 265,000 psi and a crystallization temperature of about 415"C; an amorphous metal alloy having the composition Fe74 3Cr4 5Pl5 9CsBo has an ultimate tensile strength of about 350,000 psi and a crystallization temperature of 446"C. The thermal stability of these compositions in the temperature range of 200" to 3500C is low, as evidenced by a tendency to embrittle after heat treating, for example, at 3300C for 5 minutes. Such heat treatment is required in certain specific applications, such as curing a coating of polytetrafluoroethylene on razor blade edges.
We have now found that the resistance to embrittlement upon heat treatment of these alloys in the temperature range of 200 to 350"C for several minutes is improved by replacing phosphorus with boron or boron plus at least one of the metalloid elements of carbon, silicon and aluminum.
Specifically, a class of amorphous metal alloys of the invention consists of the composition MaXb, where M is at least one element selected from iron, nickel, cobalt and chromium,
X is boron plus at least one element selected from carbon, silicon and aluminum, "a" ranges from 75 to 85 atom percent and "b" ranges from 15 to 25 atom percent.
For these amorphous metal alloys, ease of glass formation occurs where "b" ranges from 17 to 22 atom percent. Optimum thermal stability is achieved with compositions where 60 to 80 atom percent of X is boron. Accordingly, such compositions are preferred.
A preferred sub-class of these alloys is those wherein the transition metal M consists of iron, and optionally, one or more of nickel, chromium and cobalt.
The properties of corrosion resistance, hardness, and mechanical strength are improved in these amorphous metal alloys by including up to 20 atom percent of chromium in the total alloy composition. Preferably, chromium is present in an amount of 5 to 15 atom percent of the total alloy composition for optimum improvement.
Glass formation is aided in these amorphous metal alloys by including up to 30 atom percent of cobalt. Preferably, cobalt is present in an amount of 15 to 25 atom percent of the total alloy composition for optimum ease of glass formation.
Another class of amorphous metal alloys of the invention consist of the composition
MaXb, where M is at least three elements selected from iron, nickel, cobalt and chromium, the amount of each of iron, nickel and cobalt is from 20 to 35 atom percent, preferably from 20 to 30 atom percent, and the amount of chromium from 5 to 20 atom percent, preferably from 5 to 15 atom percent, and where "a" is from 75 to 85 atom percent and "b" from 15 to 25 atom percent. Preferably, "b" is from 17 to 22 atom percent. Examples include
Fe30Ni30CO20B20, Fe30Ni30CO23B17 and Fe30Ni32Cr20Bl8.
Such amorphous metal alloys containing boron alone evidence superior strength over compositions which include phosphorus. For example, an amorphous metal alloy having the composition Fe25Ni25Co20Crl0B8Pl2 has an ultimate tensile strength of 330,000 psi. Changing the metalloid content to -B 16P4 increases the ultimate tensile strength to 395,000 psi.
Where the metalloid content is -B20, the ultimate tensile strength is increased to 500,000 psi. The crystallization temperature is also observed to increase from 4610C for Fe25Ni25Co20Crl0B8Pl2 to 4850C for Fe25Ni25CO20Cr10B20. These amorphous metal alloys in which boron is the only "metalloid" element are also characterized by high hardness values, which are typically about 1000 DPH.
The amorphous metal alloys in accordance with the invention can be made by a process which comprises forming a melt of the desired composition and quenching it at a rate of 105 to 1060C/sec. Shaped articles can be made by casting the molten alloy onto a chill wheel. A variety of techniques is available, as is now well-known in the art, for fabricating splatquenched foils and rapid-quenched continuous ribbons, wire, sheet. Typically, a particular composition is selected, powders of the requisite elements (or of materials that decompose to form the elements, such as ferroboron, ferrosilicon) in the desired proportions are melted and homogenized, and the molten alloy is rapidly quenched either on a chill surface, such as a rotating cylinder, or in a suitable fluid medium, such as a chilled brine solution. The amorphous metal alloys may be formed in air. However, superior physical and mechanical properties are achieved by forming these amorphous metal alloys in a partial vacuum with absolute pressure less than about 5.5 cm of Hg, and preferably lO,am to 1 cm of Hg, as disclosed in Application No. 7222/76 (Serial No. 1,540,771). The purity of all materials is that found in normal commercial practice.
While as stated earlier the amorphous metal alloys are at least 50% amorphous, and preferably at least 80% amorphous, a substantial degree of amorphousness approaching 100% amorphous is obtained by forming these amorphous metal alloys in a partial vacuum.
Ductility is thereby improved, and such alloys possessing a substantial degree of amorphousness are accordingly preferred.
The amorphous metal alloys of the invention evidence superior fabricability, compared with conventional prior art alloys. Thus, they have improved resistance to embrittlement upon heat treatment; they do not become brittle to bending upon heating to temperatures typically employed in subsequent processing. They also have increased mechanical strength and tend to be more oxidation- and corrosion-resistant than many conventional prior art alloys.
The alloys of the invention remain amorphous at heat-treating conditions under which phosphorus-containing amorphous alloys tend to embrittle. Ribbons of these alloys find use in applications requiring relatively higher thermal stability and increased mechanical strength.
The invention therefore also provides a process of heat-treating a metal alloy which is at least 50% amorphous, the alloy being of either class having a composition MaXb as defined above, which process comprises heating the alloy to a temperature of from 200 to 3500C and at which it remains ductile.
EXAMPLES
Rapid melting and fabrication of amorphous strips of ribbon of uniform width and thickness from high melting (1100 to 1600"C) reactive alloys was accomplished under vacuum. The application of vacuum minimized oxidation and contamination of the alloy during melting or squirting and also eliminated surface damage (blisters, bubbles) commonly observed in strips processed in air or inert gas at 1 atm. A copper cylinder was mounted vertically on a shaft and placed in a stainless steel vacuum chamber. The vacuum chamber was a cylinder flanged at two ends with two side ports and was connected to a diffusion pumping system. The shaft was coupled to variable speed electric motor via a rotary feed-through device which enables the drive to be transmitted without loss of vacuum. A crucible surrounded by an induction coil assembly was located above the rotating cylinder inside the chamber. An induction power supply was used to melt alloys contained in crucibles made of fused quartz, boron nitride, alumina, zirconia or beryllia. The amorph- ous ribbons were prepared by melting the alloy in a suitable non-reacting crucible and ejecting the melt by overpressure of argon through an orifice in the bottom of the crucible onto the surface of the rotating (1500 to 2000 rgm) cylinder. The melting and squirting were carried out in a partial vacuum of about 10- pm, using an inert gas such as argon to adjust the vacuum pressure. The amorphous ribbons were subsequently tested for ultimate tensile strength.
Using the vacuum-melt casting apparatus described above, a number of various glassforming metal alloys were chill cast as continuous ribbons having substantially uniform thickness and width. Typically, the thickness ranged from 0.001 to 0.003 inch and the width ranged from 0.05 to 0.12 inch.
The mechanical behavior as a function of heat treatment conditions of amorphous metal alloys having compositions in accordance with the invention was compared with that of phosphorus-containing amorphous metal alloys. All alloys were fabricated by the process given above. The amorphous ribbons of the alloys of this invention were all ductile in the as-quenched condition, and remained so upon heat treatment within the range of 200 to 350"C for several minutes. This was in contrast with ribbons af amorphous alloys which included phosphorus as a metalloid element, which evidenced embrittlement under the same conditions of heat treatment. The ductility of the ribbons in the as-quenched and heat treated conditions was determined as follows. The ribbons were bent end on end to form a loop. The diameter of the loop was gradually reduced between the anvils of a micrometer.
The ribbons were considered ductile if they could be bent to a radius of curvature less than about 0.005 inch without fracture. If a ribbon fractured, it was considered to be brittle.
Table I lists the results of these tests.
TABLE I
Ductility Of Certain
Amorphous Metal Alloys As A Function ofHeat Treatment
Heat Treatment
Alloy Composition 200"C, 250"C, 325"C, 350"C, (Atom Percent) 90 min 90 min 5 min 10 min
Fe28Ni30Co20B ,8C2Al2 ductile ductile ductile brittle Fe2Ni4Pt4B6Si2 * brittle brittle brittle brittle
Time at Temperature of Heat Treatment
of 255 to 260"C 10 min 30 min 60 min Fe3 0Ni3 0Co20B18 Si2 ductile ductile ductile Fe30Ni30Co20P 13B 5Si2 * brittle brittle brittle
Temperature of Heat Treatment
For Time of 30 min 225"C 255 C 270"C 2900C Fe30Ni30Co20B 18Si2 ductile ductile ductile ductile Fe30Ni30Co20Pl3B5Si2 * brittle brittle brittle brittle *Prior art compositions
The data on mechanical and thermal properties (ultimate tensile strength in psi; crystallization temperature in "C) of some typical amorphous metal alloys in accordance with the invention are given in Table II below.
TABLE II
Mechanical and Thermal Properties
of Amorphous Metal Alloys
Alloy Composition Ultimate Tensile Crystallization
(Atom Percent) Strength (psi) Temperature ("C) *
(a) Fe77B13C5Si1Al2 486,ooh 510
(b) Fe66Cr12B13C5Si2 434,000 550
(c) Fe60Cr18B15C55i2 438,000 578 Fe30Ni30Co20B,8Si2 403,000 478
(d) Fe28Ni30Co20B16Si4Al2 338,000 479
(e) Fe28Ni28 Co20B 18C25i2Al2 320,000 490 Fe28Ni30Co20B18C2Al2 280,000 457 Fe30Ni30Co20B17Ai3 335,000 442
(f) Fe23Ni25Co20Cr10B20 500,000 485 Fe30Ni30Co23B17 403,000 443,477 *Heating rate: 20"C/min The alloys (a) to (f) per se are not part of the present invention, having been described and claimed in our Patent Application No. 23419/78 (Serial No. 1,540,772).
Table III below shows other alloys, which per se are part of the present invention, and their properties.
Table III
Alloy Composition Hardness Crystallization
(Atom Percent) (kg/mm2) Temp Tc( C) Fe60Cr22B16Si2 1097 575 Fe57CT25B16Si2 1114 580 Fe52Cr30B16Si2 1131 Fe70CrlOBl4C4Si2 1097 524 Fe6sCr12B14C4Si2 1150 533 Fe72Cr8Bl4C4Si2 1114 516
In our earlier British Patent Application No. 7222/76 (Serial No. 1,540,771) we have described and claimed a process of forming a filamentary strand of a metal alloy, which comprises ejecting molten alloy through an orifice as a molten filamentary strand and quenching the molten strand by causing it to impinge on a rotating chilled surface in a partial vacuum at an absolute pressure not greater than 5.5 cm of mercury. Among the alloys described therein as useful in this process are the following, which are claimed per se in Patent Application No. 23419/78 (Serial No. 1,540,772) which is a divisional of Patent
Application No. 7222/76 (Serial No. 1,540,771).
(1) Alloys which are at least 50% amorphous, as measured by X-ray diffraction, consisting of (i) 75 to 85 atom percent iron or 10 to 15 atom percent chromium and 60 to 75 atom percent iron to make a total of 75 to 85 atom percent iron plus chromium, (ii) 12 to 15 atom percent boron, (iii) 5 to 7 atom percent carbon, (iv) 1 to 4 atom percent silicon and (v) 1 to 2 atom percent aluminium.
(2) Each of the following alloys, which are at least 50% amorphous, as measured by X-ray diffraction: Fe77B 13CsSi1Al2
Fe66Cr12B 1C3Si2
Fe60Cr18B 15C5Si2
Fe28Ni30Go20B16Si4A12 Fe28Ni28Co20B ,8C2Si2Al2 Fe25Ni25CO2OCrlOB2 We make no claim herein to these alloys per se. The alloys of the present invention are a modification thereof which have been found to have high crystallisation temperatures making them valuable in uses where the alloys have to withstand prolonged heat-treatment.
In our earlier British Patent Application No. 8342/77 (Serial No. 1558151) we have described and claimed a class of magnetic amorphous alloys which have the composition (CoxFel-x)aBbC, where "x" is from 0.84 to 1.0, "a", "b" and "c" are atomic percentages totalling 100%, "a" is from 78 to 85 percent, "b" is from 10 to 22 percent and "c" is from 0 to 12 percent, with the proviso that the sum of "b" and "c" is from 15 to 22 percent. Two of the specific alloys disclosed therein have compositions within the above-defined MaXb composition, namely Co74Fe6B14C6 (which formula we regard as encompassing Co736Fe6.4B14C6) and Co74Fe6B16C4. We make no claim here to these alloysperse.
Subject to the foregoing disclaimers of alloys claimed in Patent Applications No.
23419/78 (Serial No. 1,540,772) and 8342/77 (Serial No. 1558151): WHAT WE CLAIM IS:
1. A metal alloy which is at least 50% amorphous and has the composition MaXb, wherein "a" is from 75 to 85 atom percent, and "b" is from 15 to 25 atom percent, and either (a) M represents at least one element selected from iron, nickel, chromium and cobalt and X represents boron plus at least one element selected from carbon, silicon and aluminium or (b) M represents at least three elements selected from iron, nickel, cobalt and chromium, the proportions of each of iron, nickel and cobalt, when present, being from 20 to 35 atom percent and the proportion of chromium, when present, being from 5 to 20 atom percent and X represents boron.
2. An alloy according to claim 1 of type (a) in which from 60 to 80 atom percent of X is boron.
3. An alloy according to claim 1 or 2 of type (a) containing chromium in a proportion of up to 20 atom percent of the alloy composition.
4. An alloy according to claim 1 or 2 of type (a) containing cobalt in a proportion of up to 30 atom percent of the alloy composition.
5. An alloy according to claim 1 of type (b) in which the proportion of each of iron, nickel and cobalt, when present, is from 20 to 30 atom percent and the proportion of chromium, when present, is from 5 to 15 atom percent and in which "b" is from 17 to 22 atom percent.
6. Each of the alloys according to claim 1 having a composition specifically hereinbefore defined except in Table III.
7. A process of heat-treating a metal alloy which is at least 50% amorphous, the alloy having a composition MaXb wherein "a" is from 75 to 85 atom percent, and "b" is from 15 to 25 atom percent, and either (a) M represents at least one element selected from iron, nickel, chromium and cobalt and X represents boron plus at least one element selected from carbon, silicon and aluminium or (b) M represents at least three elements selected from iron, nickel, cobalt and chromium, the proportions of each of iron, nickel and cobalt, when present, being from 20 to 35 atom percent and the proportion of chromium, when present, being from 5 to 20 atom percent and X represents boron, which process comprises heating the alloy to a temperature of from 200 to 350"C and at which it remains ductile.
8. A process according to claim 7, wherein the alloy has a composition specifically hereinbefore identified except in Table III.
9. Shaped articles comprising amorphous metal alloy when prepared by a process claimed in claim 7 or 8.
10. Each of the alloys according to claim 1 having a composition specifically hereinbefore identified in Table III.
11. A process of heat-treating an alloy according to claim 7, wherein the composition of the alloy is any one of those shown in Table III hereinbefore.
12. Shaped articles comprising amorphous metal alloy when prepared by a process claimed in claim 11.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (12)
- **WARNING** start of CLMS field may overlap end of DESC **.the specific alloys disclosed therein have compositions within the above-defined MaXb composition, namely Co74Fe6B14C6 (which formula we regard as encompassing Co736Fe6.4B14C6) and Co74Fe6B16C4. We make no claim here to these alloysperse.Subject to the foregoing disclaimers of alloys claimed in Patent Applications No.23419/78 (Serial No. 1,540,772) and 8342/77 (Serial No. 1558151): WHAT WE CLAIM IS: 1. A metal alloy which is at least 50% amorphous and has the composition MaXb, wherein "a" is from 75 to 85 atom percent, and "b" is from 15 to 25 atom percent, and either (a) M represents at least one element selected from iron, nickel, chromium and cobalt and X represents boron plus at least one element selected from carbon, silicon and aluminium or (b) M represents at least three elements selected from iron, nickel, cobalt and chromium, the proportions of each of iron, nickel and cobalt, when present, being from 20 to 35 atom percent and the proportion of chromium, when present, being from 5 to 20 atom percent and X represents boron.
- 2. An alloy according to claim 1 of type (a) in which from 60 to 80 atom percent of X is boron.
- 3. An alloy according to claim 1 or 2 of type (a) containing chromium in a proportion of up to 20 atom percent of the alloy composition.
- 4. An alloy according to claim 1 or 2 of type (a) containing cobalt in a proportion of up to 30 atom percent of the alloy composition.
- 5. An alloy according to claim 1 of type (b) in which the proportion of each of iron, nickel and cobalt, when present, is from 20 to 30 atom percent and the proportion of chromium, when present, is from 5 to 15 atom percent and in which "b" is from 17 to 22 atom percent.
- 6. Each of the alloys according to claim 1 having a composition specifically hereinbefore defined except in Table III.
- 7. A process of heat-treating a metal alloy which is at least 50% amorphous, the alloy having a composition MaXb wherein "a" is from 75 to 85 atom percent, and "b" is from 15 to 25 atom percent, and either (a) M represents at least one element selected from iron, nickel, chromium and cobalt and X represents boron plus at least one element selected from carbon, silicon and aluminium or (b) M represents at least three elements selected from iron, nickel, cobalt and chromium, the proportions of each of iron, nickel and cobalt, when present, being from 20 to 35 atom percent and the proportion of chromium, when present, being from 5 to 20 atom percent and X represents boron, which process comprises heating the alloy to a temperature of from 200 to 350"C and at which it remains ductile.
- 8. A process according to claim 7, wherein the alloy has a composition specifically hereinbefore identified except in Table III.
- 9. Shaped articles comprising amorphous metal alloy when prepared by a process claimed in claim 7 or 8.
- 10. Each of the alloys according to claim 1 having a composition specifically hereinbefore identified in Table III.
- 11. A process of heat-treating an alloy according to claim 7, wherein the composition of the alloy is any one of those shown in Table III hereinbefore.
- 12. Shaped articles comprising amorphous metal alloy when prepared by a process claimed in claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3622877A GB1572284A (en) | 1977-11-08 | 1977-11-08 | Amorphous metal alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3622877A GB1572284A (en) | 1977-11-08 | 1977-11-08 | Amorphous metal alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1572284A true GB1572284A (en) | 1980-07-30 |
Family
ID=10386166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB3622877A Expired GB1572284A (en) | 1977-11-08 | 1977-11-08 | Amorphous metal alloys |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB1572284A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163695A1 (en) * | 1983-11-14 | 1985-12-11 | Gen Electric | Heating amorphous metal to facilitate cutting. |
| US5043027A (en) * | 1987-12-05 | 1991-08-27 | Gkss-Forschungszentrum Geesthacht Gmbh | Method of reestablishing the malleability of brittle amorphous alloys |
| WO2007088951A1 (en) * | 2006-01-31 | 2007-08-09 | Nippon Steel Corporation | Alloy for liquid-phase diffusion bonding |
-
1977
- 1977-11-08 GB GB3622877A patent/GB1572284A/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163695A1 (en) * | 1983-11-14 | 1985-12-11 | Gen Electric | Heating amorphous metal to facilitate cutting. |
| EP0163695A4 (en) * | 1983-11-14 | 1987-01-20 | Gen Electric | Heating amorphous metal to facilitate cutting. |
| US5043027A (en) * | 1987-12-05 | 1991-08-27 | Gkss-Forschungszentrum Geesthacht Gmbh | Method of reestablishing the malleability of brittle amorphous alloys |
| WO2007088951A1 (en) * | 2006-01-31 | 2007-08-09 | Nippon Steel Corporation | Alloy for liquid-phase diffusion bonding |
| JP2008119744A (en) * | 2006-01-31 | 2008-05-29 | Nippon Steel Corp | Alloy for liquid-phase diffusion bonding |
| KR101004909B1 (en) | 2006-01-31 | 2010-12-28 | 신닛뽄세이테쯔 카부시키카이샤 | Alloy for liquid-phase diffusion bonding |
| CN101374631B (en) * | 2006-01-31 | 2012-04-18 | 新日本制铁株式会社 | Alloy for liquid-phase diffusion bonding |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19960223 |