CA1048815A - Amorphous alloys with high crystallization temperatures and high hardness values - Google Patents
Amorphous alloys with high crystallization temperatures and high hardness valuesInfo
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- C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
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Abstract
INVENTORS: RANJAN RAY, LEE E. TANNER and CARL F. CLINE
INVENTION: AMORPHOUS ALLOYS WITH HIGH CRYSTALLIZATION
TEMPERATURES AND HIGH HARDNESS VALUES
ABSTRACT OF THE DISCLOSURE
Amorphous metal-matalloid alloys having substantial amounts of one or more of the elements of Mo, W, Ta and Nb evi-dence both high thermal stability, with crystallization tempera-tures ranging from about 650°C to 975°C, and high hardness, with values ranging from about 800 to 1400 DPH (diamond pyramid hard-ness). The alloys are useful as electrodes in high temperature electrolytic cells, reinforcement fibers in composite structural materials and other applications requiring heat resistant proper-ties high temperatures.
INVENTION: AMORPHOUS ALLOYS WITH HIGH CRYSTALLIZATION
TEMPERATURES AND HIGH HARDNESS VALUES
ABSTRACT OF THE DISCLOSURE
Amorphous metal-matalloid alloys having substantial amounts of one or more of the elements of Mo, W, Ta and Nb evi-dence both high thermal stability, with crystallization tempera-tures ranging from about 650°C to 975°C, and high hardness, with values ranging from about 800 to 1400 DPH (diamond pyramid hard-ness). The alloys are useful as electrodes in high temperature electrolytic cells, reinforcement fibers in composite structural materials and other applications requiring heat resistant proper-ties high temperatures.
Description
1~4~3815 AMORPHOUS ALLOYS WITH HIGH CRYSTALLIZATION
TEMPERATURES AND HIGH HARDNESS VALUES
Background of the Invention A. Field of the Invention .
The invention relates to amorphous metal alloy composi-tions, and, in particular, to compositions including substantial amounts of one or more of the elements of Mo, W, Ta and Nb, which evidence both high crystallization temperatures and high hardness values.
B. Description of the Prior Art Investigations have demonstrated that it is possible to obtain solid amorphous metals for certain alloy compositions, and as used herein, the term "amorphous" contemplates "solid amorphous". An amorphous substance generally characterizes a noncrystalline or glass substance; that is, a substance substan-tially lacking any long range order. In distinguishing an amor-phous substance from a crystalline substance, X-ray diffraction measurements are generally suitably employed. Additionally, trans-mission electron micrography and electron diffraction can be used to distinguish between the amorphous and the crystallizine 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 crystal-line 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 diffraction profile changes from one having glassy or amorphous characteristics to one having crystalline characteristics.
It is possible to produce a metal which is a two phase p~, ' ~
1~48~315 mixture of the amorphous and the crystalline state; the relative proportions can vary from totally crystalline to totally amorphous.
An amorphous metal, as employed herein, refers to a metal which is primarily amorphous; that is, at least 50~ amorphous, but which may have a small fraction of the material present as included crystallites.
For a suitable composition, proper processing will produce a metal in the amorphous state. One typical procedure is to cause the molten alloy to be spread thinly in contact with a solid metal substrate, such as copper or aluminum, so that the molten metal rapidly loses its heat to the substrate.
When the alloy is spread to a thickness of about 0.002 inch, cooling rates of the order of 106C/sec may be achieved.
See, for example, R. C. Ruhl, Vol. 1, Mat. Sci. & Eng., pp. 313-319 (1967), which discusses the dependence of cooling rates upon the conditions of processing the molten metal. For an alloy of proper composition and for a sufficiently high cooling rate, such a process produces an amorphous metal. Any process which provides a suitably high cooling rate can be used. Illustrative examples of procedures which can be used to make the amorphous metals in-clude rotating double rolls, as described by H. S. Chen and C. E.
Miller, Vol. 41, Rev. Sci. Instrum., pp. 1237-1238 (1970), and rotating cylinder techniques, as described by R. Pond, Jr. and R.
Maddin, Vol. 245, Trans. Met. Soc., AIME, pp. 2475-2476 (1969).
Amorphous alloys containing substantial amounts of one or re of the elements of Fe, Ni, Co, V and Cr have been de-scribed by H~ S. Chen and D. E. Polk in United States Patent No.
3,856,513, issued December 24, 1974. Such alloys are quite useful for a variety of applications. Such alloys, however, are charac-30 terized by a crystallization temperature of about 425C to 550C
and a hardness of about 600 to 750 DPH (diamond _yramid hardness).
1~41~815 Summary of the Invention In accordance with the invention, amorphous alloys are described having high thermal stability, with crystallization temperatures ranging from about 650C to 975C and high hardness, with values ranging from about 800 to 1400 DPH. Two general compositions have these properties and may be classified as follows. The first class of compositions is referred to as metal-metalloid, and has the general formula RrMSXt, where R is at least one of the elements of molybdenum, tungsten, tantalum, and niobium, M is at least one of the elements of nickel, chromium, iron, vanadium, aluminum and cobalt, and X is at least one of the elements of phosphorus, boron, carbon and silicon, and where "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent and "t" ranges from about 15 to 25 atom percent. Preferred compositions include compositions where "r" ranges from about 45 to 55 atom percent, "s" ranges from about 25 to 35 atom percent and "t" ranges from about 18 to 22 atom percent. The crystalliza-tion temperature of the metal-metalloid compositions ranges from about 800C to 975C and the hardness ranges from about 1000 to 20 1400 DPH.
The second classification is referred to as metal-metal, and includes refractory metal-base glasses of the general formula RrNiSTt, where R is at least one of the elements of tantalum, -niobium and tungsten and T is at least one of the elements of titanium and zirconium, and where "r" ranges from about 35 to 65 atom percent, "s" ranges from about 25 to 65 atom percent and "t" ranges from 0 to about 15 atom percent. Preferred compositions, where "t" is 0, include the composition region encompassed from Ta35NiSW65-s to Ta45Nisw55-s~ where "s" ranges from about 35 to 30 45 atom percent, and the composition TarNis, where "r" ranges from about 35 to 50 atom percent and "s" ranges from about 50 to 65 atom percent. The crystallization temperature of the metal-metal ~6)48815 compositions ranges from about 650C to 800C, and the hardness ranges from about 800 to 1125 DPH.
Such metal glasses, whether metal-metalloid or metal-metal, are particularly useful for heat resistant applications at high temperatures (about 500 to 600C). Possible applications include use of these materials as electrodes in certain high temperature electrolytic cells, and as reinforcement fibers in composite structural materials.
Brief Description of the Drawing FIG. 1 is a ternary phase diagram in atom percent of the metal-metalloid system R-M-X, where R is one or more of the elements of Mo, w, Ta and Nb, M is one or more of the elements of Ni, Cr, Fe, V, Al and Co and X is one or more of the elements of P, B, C and Si; and FIG. 2 is a ternary phase diagram in atom percent of the metal-metal system Ta-W-Ni.
Detailed Description of the Invention A. Metal-Metalloid Compositions Most liquid-quenched glass compositions in various metal-metalloid systems have evidenced crystallization temperatures of about 425C to 550C. In accordance with the present invention, compositions represented by the general formula RrMSxt have crys-tallization temperatures ranging from about 800C to 975C. In the formula, R is at least one of the refractory metals of Mo, W, Ta and Nb, M is at least one of the metals of Ni, Cr, Fe, V, Al and Co and X is at least one of the metalloids of P, B, C
and Si. The purity of all elements described is that found in normal commercial practice.
For Mo-base compositions, amorphous alloys are formed in systems containing at least about 25 atom percent of Ni, Cr, Fe, V or Al Typical compositions in atom percent are Mo52CrlOFelONig-P12B8 and M40Cr25Fel5B8C7Sis- Such amorphous alloys, or glasses, - 1~)48815 :
possess high thermal stability as revealed by DTA (_ifferential thermal analysis) investigation. The temperatures for crystalli-zation peaks, Tc, can be accurately determined from DTA by slowly heating the glass sample and noting whether excess heat is evolved at a particular temperature (crystallization temperature) or whether excess heat is absorbed over a particular temperature range (glass transition temperature). In general, the less well-defined glass transition temperature Tg is considered to be within about 50 below the lowest, or first, crystallization peak, TC1~ and, as is conventional, encompasses the temperature region over which the viscosity ranges from about 1013 to 1014 poise.
The various Mo-base glasses with about 25 to 32 atom percent Ni, Cr, Fe, Al (either single or combined), plus about 12 atom percent P and about 8 atom percent B, crystallize in the range of about 800C to 900C. Substitution of P by C or Si by 6 to 8 atom percent increases Tc by about 40C to 50C. Further thermal stability is achieved by partial substitution of W for Mo. Alloys containing about 8 to 20 atom percent W have crystallization tempera-tures in the range of about 900C to 950C.
High Tg glass-forming compositions exist also in W-base alloys. Typically, these alloys contain about 15 to 25 atom per-cent Mo, about 25 atom percent Ni, Fe, and Cr, and about 20 atom percent P, B, C and Si. These alloy glasses are remarkably stable and crystallize at temperatures in excess of 950C. For example, one glass composition, W40Mol5CrlsFesNi5P6B6C5Si3, evidences two crystallization peaks, 960C and 980C, in a DTA trace. However, as W content is increased to beyond 40 atom percent, it becomes increasingly difficult to form a glass.
The glasses are formed by cooling a melt at a rate of about 105 to 106C/min. A variety of techniques are available, as is well-known in the art, for fabricating splat-quenched foils and rapid-quenched continuous ribbon, wire, etc.
.. . ..
-: , :
. . , - , ' . . , ',' . : - ' : - :
~4~8~5 Glasses evidencing high Tg properties as described above also evidence high ductility and high corrosion resistance compared to crystalline or partially crystalline samples. In addition, these amorphous alloys have rather high hardness values.
Typically, the hardness for Mo- and W-base glasses ranges from about 1000 to 1400 DPH (diamond _yramid hardness). This is to be com-pared with amorphous alloys of metal-metalloid compositions comprising substantial amounts of Fe or Fe-Ni, but lacking any substantial amount of refractory metal. For these latter alloys, 10 the hardness usually is about 600 to 750 DPH.
Shown in FIG. 1 is a ternary phase diagram of the system R-M-X, where R is Mo, W, Ta and/or Nb, M is Ni, Cr, Fe, V, Al and/or Co, and X is P, B, C and/or Si. The polygonal region designated a-b-c-d-e-f-a encloses the glass-forming region that also includes composition having high Tg and high hardness. Outside this composi-tion region, either a substantial degree of amorphousness is not attained or the beneficial properties are unacceptably reduced.
The compositional boundaries of the polygonal region are described as follows: "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent, and "t"
ranges from about 15 to 25 atom percent. The highest values of Tg and hardness are formed in compositions represented by the "line" g-h, that is, in which "r" ranges from about 45 to 55 atom percent, "s" ranges from about 25 to 35 atom percent, and "t"
ranges from about 18 to 22 atom percent (more specifically, "t"
is about 20 atom percent). Accordingly, this latter composition range is preferred. Maximum benefit is derived for compositions where R is Mo and/or W and M is Ni, Fe and/or Cr.
B. Metal-Metal Compositions Also in accordance with the present invention, alloys providing consistent glass-forming behavior plus high thermal stability include the binary systems Ta-Ni, Nb-Ni and ternary 104~815 modifications with W, Ti and/or Zr. Here, the compositions of interest may be described by the general formula RrNiSTt, where R is Ta, Nb and/or W and T is Ti and/or Zr. Such compositions have crystallization temperatures ranging from about 650C to 800C.
Ta-Ni binary glasses crystallize in the range 760c to 780C, which is about 100C higher than those for Nb-Ni glasses.
The partial substitution of W for Ta raises Tc only slightly (about 15C to 20C) and does not change appreciably with increasing W content. On the other hand, partial addition of Ti or Zr tends to lower Tc.
For the binary compositions of TarNis and NbrNiS, glasses are formed where "r" ranges from about 35 to 65 atom percent and "s" is the balance, that is, 35 to 65 atom percent (t=O). Optimum properties are obtained in the system TarNis, where "r" ranges from about 35 to 50 atom percent and "s" ranges from about 50 to 65 atom percent.
For the ternary composition region from Ta35NiSW65-S
to Ta4sNisW55_s, a glass-forming region that is consistent with 20 high Tg and high hardness is shown in FIG. 2, which is a ternary phase diagram of the system Ta-W-Ni. The polygonal region desig-nated a-b-c-d-a encompasses the optimum glass-forming region.
Outside this composition region, either a substantial degree of amorphousness is now attained or the beneficial properties are unacceptably reduced. In FIG. 2, "s" ranges from about 35 to 45 atom percent.
Since the addition of Ti or Zr tends to lower Tc, then such addition should not exceed about 15 atom percent, and preferably 10 percent, to retain the advantages of high Tg and 30 high hardness.
In general, the hardness of the foregoing systems ranges from about 800 to 1125 DPH.
1~488~5 EXAMPLES
A. Metal-Metalloid Compositions A pneumatic arc-splat unit for melting and liquid quenching high temperature reactive alloys was used. The unit, which was a conventional arc-melting button furnace modified to provide "hammer and anvil" splat quenching of alloys under inert atmosphere, included a stainless steel chamber connected with a 4 inch diffusion pumping system. The quenching was accomplished by providing a flat-surfaced water-cooled copper hearth on the floor of the chamber and a pneumatically driven copper-block hammer poised above the molten alloy. As is conventional, arc-melting was accomplished by negatively biasing a copper shaft provided with a tungsten tip inserted through the top of the chamber and by positively biasing the bottom of the chamber. Alloys containing P were prepared by sintering powder ingredients followed by arc-melting to homogenization. All other alloys were prepared directly by repeated arc-melting of constituent elements. A single alloy button (about 200 mg) was remelted and then "impact-quenched" into a foil about 0.004 inch thick by the hammer situated just above the molten pool. The cooling rate attained by this technique was about 105 to 106C/sec. The foils were checked for amorphous-ness by X-ray diffraction and DTA.
The impact-quenched foil directly beneath the hammer may have suffered plastic deformation after solidification.
However, portions of the foil formed from the melt spread away from the hammer were undeformed and hence suitable for hardness and other related tests. Hardness was measured by the diamond pyramid technique, using a Vickers-type indenter consisting of a diamond in the form of a square-based pyramid with an included angle to 136 between opposite faces.
The crystallization temperatures and hardness values are shown in Table I for a variety of metal-metalloid compositions.
. : , .
16~488~5 TABLE I
CRYSTALLIZATION TEMPERATURES (TC1) AND HARDNESS (DPH) MEASUREMENTS
FOR METAL-METALLOID COMPOSITIONS
Composition Hardness, Example atom % _cl~__C DPH
1 M48Cr32Pl2B8 878 ----
TEMPERATURES AND HIGH HARDNESS VALUES
Background of the Invention A. Field of the Invention .
The invention relates to amorphous metal alloy composi-tions, and, in particular, to compositions including substantial amounts of one or more of the elements of Mo, W, Ta and Nb, which evidence both high crystallization temperatures and high hardness values.
B. Description of the Prior Art Investigations have demonstrated that it is possible to obtain solid amorphous metals for certain alloy compositions, and as used herein, the term "amorphous" contemplates "solid amorphous". An amorphous substance generally characterizes a noncrystalline or glass substance; that is, a substance substan-tially lacking any long range order. In distinguishing an amor-phous substance from a crystalline substance, X-ray diffraction measurements are generally suitably employed. Additionally, trans-mission electron micrography and electron diffraction can be used to distinguish between the amorphous and the crystallizine 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 crystal-line 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 diffraction profile changes from one having glassy or amorphous characteristics to one having crystalline characteristics.
It is possible to produce a metal which is a two phase p~, ' ~
1~48~315 mixture of the amorphous and the crystalline state; the relative proportions can vary from totally crystalline to totally amorphous.
An amorphous metal, as employed herein, refers to a metal which is primarily amorphous; that is, at least 50~ amorphous, but which may have a small fraction of the material present as included crystallites.
For a suitable composition, proper processing will produce a metal in the amorphous state. One typical procedure is to cause the molten alloy to be spread thinly in contact with a solid metal substrate, such as copper or aluminum, so that the molten metal rapidly loses its heat to the substrate.
When the alloy is spread to a thickness of about 0.002 inch, cooling rates of the order of 106C/sec may be achieved.
See, for example, R. C. Ruhl, Vol. 1, Mat. Sci. & Eng., pp. 313-319 (1967), which discusses the dependence of cooling rates upon the conditions of processing the molten metal. For an alloy of proper composition and for a sufficiently high cooling rate, such a process produces an amorphous metal. Any process which provides a suitably high cooling rate can be used. Illustrative examples of procedures which can be used to make the amorphous metals in-clude rotating double rolls, as described by H. S. Chen and C. E.
Miller, Vol. 41, Rev. Sci. Instrum., pp. 1237-1238 (1970), and rotating cylinder techniques, as described by R. Pond, Jr. and R.
Maddin, Vol. 245, Trans. Met. Soc., AIME, pp. 2475-2476 (1969).
Amorphous alloys containing substantial amounts of one or re of the elements of Fe, Ni, Co, V and Cr have been de-scribed by H~ S. Chen and D. E. Polk in United States Patent No.
3,856,513, issued December 24, 1974. Such alloys are quite useful for a variety of applications. Such alloys, however, are charac-30 terized by a crystallization temperature of about 425C to 550C
and a hardness of about 600 to 750 DPH (diamond _yramid hardness).
1~41~815 Summary of the Invention In accordance with the invention, amorphous alloys are described having high thermal stability, with crystallization temperatures ranging from about 650C to 975C and high hardness, with values ranging from about 800 to 1400 DPH. Two general compositions have these properties and may be classified as follows. The first class of compositions is referred to as metal-metalloid, and has the general formula RrMSXt, where R is at least one of the elements of molybdenum, tungsten, tantalum, and niobium, M is at least one of the elements of nickel, chromium, iron, vanadium, aluminum and cobalt, and X is at least one of the elements of phosphorus, boron, carbon and silicon, and where "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent and "t" ranges from about 15 to 25 atom percent. Preferred compositions include compositions where "r" ranges from about 45 to 55 atom percent, "s" ranges from about 25 to 35 atom percent and "t" ranges from about 18 to 22 atom percent. The crystalliza-tion temperature of the metal-metalloid compositions ranges from about 800C to 975C and the hardness ranges from about 1000 to 20 1400 DPH.
The second classification is referred to as metal-metal, and includes refractory metal-base glasses of the general formula RrNiSTt, where R is at least one of the elements of tantalum, -niobium and tungsten and T is at least one of the elements of titanium and zirconium, and where "r" ranges from about 35 to 65 atom percent, "s" ranges from about 25 to 65 atom percent and "t" ranges from 0 to about 15 atom percent. Preferred compositions, where "t" is 0, include the composition region encompassed from Ta35NiSW65-s to Ta45Nisw55-s~ where "s" ranges from about 35 to 30 45 atom percent, and the composition TarNis, where "r" ranges from about 35 to 50 atom percent and "s" ranges from about 50 to 65 atom percent. The crystallization temperature of the metal-metal ~6)48815 compositions ranges from about 650C to 800C, and the hardness ranges from about 800 to 1125 DPH.
Such metal glasses, whether metal-metalloid or metal-metal, are particularly useful for heat resistant applications at high temperatures (about 500 to 600C). Possible applications include use of these materials as electrodes in certain high temperature electrolytic cells, and as reinforcement fibers in composite structural materials.
Brief Description of the Drawing FIG. 1 is a ternary phase diagram in atom percent of the metal-metalloid system R-M-X, where R is one or more of the elements of Mo, w, Ta and Nb, M is one or more of the elements of Ni, Cr, Fe, V, Al and Co and X is one or more of the elements of P, B, C and Si; and FIG. 2 is a ternary phase diagram in atom percent of the metal-metal system Ta-W-Ni.
Detailed Description of the Invention A. Metal-Metalloid Compositions Most liquid-quenched glass compositions in various metal-metalloid systems have evidenced crystallization temperatures of about 425C to 550C. In accordance with the present invention, compositions represented by the general formula RrMSxt have crys-tallization temperatures ranging from about 800C to 975C. In the formula, R is at least one of the refractory metals of Mo, W, Ta and Nb, M is at least one of the metals of Ni, Cr, Fe, V, Al and Co and X is at least one of the metalloids of P, B, C
and Si. The purity of all elements described is that found in normal commercial practice.
For Mo-base compositions, amorphous alloys are formed in systems containing at least about 25 atom percent of Ni, Cr, Fe, V or Al Typical compositions in atom percent are Mo52CrlOFelONig-P12B8 and M40Cr25Fel5B8C7Sis- Such amorphous alloys, or glasses, - 1~)48815 :
possess high thermal stability as revealed by DTA (_ifferential thermal analysis) investigation. The temperatures for crystalli-zation peaks, Tc, can be accurately determined from DTA by slowly heating the glass sample and noting whether excess heat is evolved at a particular temperature (crystallization temperature) or whether excess heat is absorbed over a particular temperature range (glass transition temperature). In general, the less well-defined glass transition temperature Tg is considered to be within about 50 below the lowest, or first, crystallization peak, TC1~ and, as is conventional, encompasses the temperature region over which the viscosity ranges from about 1013 to 1014 poise.
The various Mo-base glasses with about 25 to 32 atom percent Ni, Cr, Fe, Al (either single or combined), plus about 12 atom percent P and about 8 atom percent B, crystallize in the range of about 800C to 900C. Substitution of P by C or Si by 6 to 8 atom percent increases Tc by about 40C to 50C. Further thermal stability is achieved by partial substitution of W for Mo. Alloys containing about 8 to 20 atom percent W have crystallization tempera-tures in the range of about 900C to 950C.
High Tg glass-forming compositions exist also in W-base alloys. Typically, these alloys contain about 15 to 25 atom per-cent Mo, about 25 atom percent Ni, Fe, and Cr, and about 20 atom percent P, B, C and Si. These alloy glasses are remarkably stable and crystallize at temperatures in excess of 950C. For example, one glass composition, W40Mol5CrlsFesNi5P6B6C5Si3, evidences two crystallization peaks, 960C and 980C, in a DTA trace. However, as W content is increased to beyond 40 atom percent, it becomes increasingly difficult to form a glass.
The glasses are formed by cooling a melt at a rate of about 105 to 106C/min. A variety of techniques are available, as is well-known in the art, for fabricating splat-quenched foils and rapid-quenched continuous ribbon, wire, etc.
.. . ..
-: , :
. . , - , ' . . , ',' . : - ' : - :
~4~8~5 Glasses evidencing high Tg properties as described above also evidence high ductility and high corrosion resistance compared to crystalline or partially crystalline samples. In addition, these amorphous alloys have rather high hardness values.
Typically, the hardness for Mo- and W-base glasses ranges from about 1000 to 1400 DPH (diamond _yramid hardness). This is to be com-pared with amorphous alloys of metal-metalloid compositions comprising substantial amounts of Fe or Fe-Ni, but lacking any substantial amount of refractory metal. For these latter alloys, 10 the hardness usually is about 600 to 750 DPH.
Shown in FIG. 1 is a ternary phase diagram of the system R-M-X, where R is Mo, W, Ta and/or Nb, M is Ni, Cr, Fe, V, Al and/or Co, and X is P, B, C and/or Si. The polygonal region designated a-b-c-d-e-f-a encloses the glass-forming region that also includes composition having high Tg and high hardness. Outside this composi-tion region, either a substantial degree of amorphousness is not attained or the beneficial properties are unacceptably reduced.
The compositional boundaries of the polygonal region are described as follows: "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent, and "t"
ranges from about 15 to 25 atom percent. The highest values of Tg and hardness are formed in compositions represented by the "line" g-h, that is, in which "r" ranges from about 45 to 55 atom percent, "s" ranges from about 25 to 35 atom percent, and "t"
ranges from about 18 to 22 atom percent (more specifically, "t"
is about 20 atom percent). Accordingly, this latter composition range is preferred. Maximum benefit is derived for compositions where R is Mo and/or W and M is Ni, Fe and/or Cr.
B. Metal-Metal Compositions Also in accordance with the present invention, alloys providing consistent glass-forming behavior plus high thermal stability include the binary systems Ta-Ni, Nb-Ni and ternary 104~815 modifications with W, Ti and/or Zr. Here, the compositions of interest may be described by the general formula RrNiSTt, where R is Ta, Nb and/or W and T is Ti and/or Zr. Such compositions have crystallization temperatures ranging from about 650C to 800C.
Ta-Ni binary glasses crystallize in the range 760c to 780C, which is about 100C higher than those for Nb-Ni glasses.
The partial substitution of W for Ta raises Tc only slightly (about 15C to 20C) and does not change appreciably with increasing W content. On the other hand, partial addition of Ti or Zr tends to lower Tc.
For the binary compositions of TarNis and NbrNiS, glasses are formed where "r" ranges from about 35 to 65 atom percent and "s" is the balance, that is, 35 to 65 atom percent (t=O). Optimum properties are obtained in the system TarNis, where "r" ranges from about 35 to 50 atom percent and "s" ranges from about 50 to 65 atom percent.
For the ternary composition region from Ta35NiSW65-S
to Ta4sNisW55_s, a glass-forming region that is consistent with 20 high Tg and high hardness is shown in FIG. 2, which is a ternary phase diagram of the system Ta-W-Ni. The polygonal region desig-nated a-b-c-d-a encompasses the optimum glass-forming region.
Outside this composition region, either a substantial degree of amorphousness is now attained or the beneficial properties are unacceptably reduced. In FIG. 2, "s" ranges from about 35 to 45 atom percent.
Since the addition of Ti or Zr tends to lower Tc, then such addition should not exceed about 15 atom percent, and preferably 10 percent, to retain the advantages of high Tg and 30 high hardness.
In general, the hardness of the foregoing systems ranges from about 800 to 1125 DPH.
1~488~5 EXAMPLES
A. Metal-Metalloid Compositions A pneumatic arc-splat unit for melting and liquid quenching high temperature reactive alloys was used. The unit, which was a conventional arc-melting button furnace modified to provide "hammer and anvil" splat quenching of alloys under inert atmosphere, included a stainless steel chamber connected with a 4 inch diffusion pumping system. The quenching was accomplished by providing a flat-surfaced water-cooled copper hearth on the floor of the chamber and a pneumatically driven copper-block hammer poised above the molten alloy. As is conventional, arc-melting was accomplished by negatively biasing a copper shaft provided with a tungsten tip inserted through the top of the chamber and by positively biasing the bottom of the chamber. Alloys containing P were prepared by sintering powder ingredients followed by arc-melting to homogenization. All other alloys were prepared directly by repeated arc-melting of constituent elements. A single alloy button (about 200 mg) was remelted and then "impact-quenched" into a foil about 0.004 inch thick by the hammer situated just above the molten pool. The cooling rate attained by this technique was about 105 to 106C/sec. The foils were checked for amorphous-ness by X-ray diffraction and DTA.
The impact-quenched foil directly beneath the hammer may have suffered plastic deformation after solidification.
However, portions of the foil formed from the melt spread away from the hammer were undeformed and hence suitable for hardness and other related tests. Hardness was measured by the diamond pyramid technique, using a Vickers-type indenter consisting of a diamond in the form of a square-based pyramid with an included angle to 136 between opposite faces.
The crystallization temperatures and hardness values are shown in Table I for a variety of metal-metalloid compositions.
. : , .
16~488~5 TABLE I
CRYSTALLIZATION TEMPERATURES (TC1) AND HARDNESS (DPH) MEASUREMENTS
FOR METAL-METALLOID COMPOSITIONS
Composition Hardness, Example atom % _cl~__C DPH
1 M48Cr32Pl2B8 878 ----
2 Mo48Fe32Pl2B8 828 ----
3 Mo 48Ni 32 P12B8 805 ----
4 Mo5oFeloAl2oploB7si3 837 1026 10 5 MO52Crl4Fel4Pl2B8 863 1260 6 MO52crloFeloNi8Pl2 8 831 1234 7 Mo40Cr25Fel5B8C7Si5 913 ____ 8 M40Wlocr30Pl5B5 881 ----9 Mo35W20crl8Fe7p6B6c5si3 950 --Mo40W15Crl8Fe7P6B6C5Si3 894 ____ 11 M35W15Cr25Fe5P6B6C5Si3 920 ----12 Mo40W8Cr24Fe8P6B6C5Si3 902 1392 13 Mo30Nb2ocr3op8B7si5 9 3 1187 14 w30Mo25Crl8Fe7p6B6c5si3 5 1350 2015 W35MO20Crl5Fe5Ni5P6B6C5Si3 946 1378 16 W40MO15Crl5Fe5Ni5P6B6C5Si3 960 1396 B Metal-Metal Compositions .
Various metal-metal compositions were prepared and measured as described above. The results of the crystallization temperature and hardness are shown in Table II.
- ' , TABLE II
CRYSTALLIZATION TEMPERATURES (TC1) AND HARDNESS (DPH) MEASUREMENTS
FOR METAL-METAL SYSTEMS
Composition, Hardness, Example atom % _cl~ C DPH
18 Ta50Ni50 767941, 1115 19 Ta45Ni45Wlo 818, 969 Ta45Ni40Wl5 796 ____ lo 21 Ta45Ni35W2o 800 ____ 22 Ta35Ni45W2o 791 ____ 23 Ta35Ni35w3o 800 ____ 24 Ta55Ni35Zrlo 683 ____ Ta55Ni35TilO
26 Ta50Ni4oTilo 717 ____ 27 Nb65Ni35 662 960 28 Nb6oNi4o 680 923 29 Nb50Ni50 653 863 Nb60Ni28Til2 662 - --.. . . . .
' '' " ' .,, . - ,. :. .,, :;. , , .
Various metal-metal compositions were prepared and measured as described above. The results of the crystallization temperature and hardness are shown in Table II.
- ' , TABLE II
CRYSTALLIZATION TEMPERATURES (TC1) AND HARDNESS (DPH) MEASUREMENTS
FOR METAL-METAL SYSTEMS
Composition, Hardness, Example atom % _cl~ C DPH
18 Ta50Ni50 767941, 1115 19 Ta45Ni45Wlo 818, 969 Ta45Ni40Wl5 796 ____ lo 21 Ta45Ni35W2o 800 ____ 22 Ta35Ni45W2o 791 ____ 23 Ta35Ni35w3o 800 ____ 24 Ta55Ni35Zrlo 683 ____ Ta55Ni35TilO
26 Ta50Ni4oTilo 717 ____ 27 Nb65Ni35 662 960 28 Nb6oNi4o 680 923 29 Nb50Ni50 653 863 Nb60Ni28Til2 662 - --.. . . . .
' '' " ' .,, . - ,. :. .,, :;. , , .
Claims (4)
1. A metal alloy at least 50% amorphous having a high crystallization temperature and a high hardness, charac-terized in that the alloy has the composition RrMsXt, where R
is at least one of the elements selected from the group consist-ing of molybdenum, tungsten, tantalum and niobium, M is at least one of the elements selected from the group consisting of nickel, chromium, iron, vanadium, aluminum and cobalt, X is at least one of the elements selected from the group consisting of phosphorous, boron, carbon and silicon, "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent, and "t"
ranges from about 15 to 25 atom percent.
is at least one of the elements selected from the group consist-ing of molybdenum, tungsten, tantalum and niobium, M is at least one of the elements selected from the group consisting of nickel, chromium, iron, vanadium, aluminum and cobalt, X is at least one of the elements selected from the group consisting of phosphorous, boron, carbon and silicon, "r" ranges from about 40 to 60 atom percent, "s" ranges from about 20 to 40 atom percent, and "t"
ranges from about 15 to 25 atom percent.
2. The alloy of claim 1 in which "r" ranges from about 45 to 55 atom percent, "s" ranges from about 25 to 35 atom percent, and "t" ranges from about 18 to 22 atom percent.
3. The alloy of claim 1 in which R is at least one of the elements selected from the group consisting of molybdenum and tungsten and M is at least one of the elements selected from the group consisting of nickel, iron and chromium.
4. A metal alloy as in Claim 1, 2 or 3 wherein the alloy has a crystallization temperature ranging from about 800°C to 975°C and a hardness ranging from about 1000 to 1400 DPH
(diamond pyramid hardness).
(diamond pyramid hardness).
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49545874A | 1974-08-07 | 1974-08-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048815A true CA1048815A (en) | 1979-02-20 |
Family
ID=23968714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75232901A Expired CA1048815A (en) | 1974-08-07 | 1975-08-06 | Amorphous alloys with high crystallization temperatures and high hardness values |
Country Status (6)
| Country | Link |
|---|---|
| JP (2) | JPS5811500B2 (en) |
| CA (1) | CA1048815A (en) |
| DE (1) | DE2534379C2 (en) |
| FR (1) | FR2281434A1 (en) |
| GB (1) | GB1476589A (en) |
| IT (1) | IT1046075B (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856513A (en) * | 1972-12-26 | 1974-12-24 | Allied Chem | Novel amorphous metals and amorphous metal articles |
| DE2719988C2 (en) * | 1977-05-04 | 1983-01-05 | Siemens AG, 1000 Berlin und 8000 München | Amorphous metal layer containing tantalum, temperature-stable at least up to 300 degrees C, and process for its production |
| CH622380A5 (en) * | 1977-12-21 | 1981-03-31 | Bbc Brown Boveri & Cie | |
| DE2861328D1 (en) * | 1978-01-03 | 1982-01-14 | Allied Corp | Iron group transition metal-refractory metal-boron glassy alloys |
| JPS6030734B2 (en) * | 1979-04-11 | 1985-07-18 | 健 増本 | Amorphous alloy containing iron group elements and zirconium with low brittleness and excellent thermal stability |
| US4544473A (en) * | 1980-05-12 | 1985-10-01 | Energy Conversion Devices, Inc. | Catalytic electrolytic electrode |
| US4743513A (en) * | 1983-06-10 | 1988-05-10 | Dresser Industries, Inc. | Wear-resistant amorphous materials and articles, and process for preparation thereof |
| JPH0615706B2 (en) * | 1985-03-14 | 1994-03-02 | 三井造船株式会社 | High corrosion resistant amorphous alloy |
| JPS6233735A (en) * | 1985-08-06 | 1987-02-13 | Mitsui Eng & Shipbuild Co Ltd | Amorphous alloy having high corrosion resistance |
| DE3616008C2 (en) * | 1985-08-06 | 1994-07-28 | Mitsui Shipbuilding Eng | Highly corrosion-resistant, glass-like alloy |
| JPS62214148A (en) * | 1986-03-17 | 1987-09-19 | Nec Corp | Amorphous alloy |
| JPS62235448A (en) * | 1986-04-03 | 1987-10-15 | Nec Corp | Amorphous alloy |
| JPS63259043A (en) * | 1987-04-16 | 1988-10-26 | Agency Of Ind Science & Technol | Nickel based alloy for diffusion bonding and its production |
| JPS63312965A (en) * | 1987-06-16 | 1988-12-21 | Meidensha Electric Mfg Co Ltd | Highly corrosion resistant coated material |
| JPH0613743B2 (en) * | 1987-11-19 | 1994-02-23 | 工業技術院長 | Solid-state joining method for nickel-base superalloys |
| JPH03267355A (en) * | 1990-03-15 | 1991-11-28 | Sumitomo Electric Ind Ltd | Aluminum-chromium alloy and its production |
| KR100289088B1 (en) * | 1998-12-02 | 2001-05-02 | 박인복 | Method for manufacturing alloy material for electrode tip of plasma generator |
| JP6406939B2 (en) * | 2014-09-04 | 2018-10-17 | キヤノン株式会社 | Amorphous alloy, mold for molding, and method of manufacturing optical element |
| DE102018113340B4 (en) * | 2018-06-05 | 2020-10-01 | Otto-Von-Guericke-Universität Magdeburg | Density-optimized molybdenum alloy |
| DE102018115815A1 (en) * | 2018-06-29 | 2020-01-02 | Universität des Saarlandes | Device and method for producing a cast part formed from an amorphous or partially amorphous metal, and cast part |
| CN114959397B (en) * | 2022-04-28 | 2023-04-07 | 长沙惠科光电有限公司 | Alloy target material, preparation method and application thereof, and array substrate |
| WO2024046742A1 (en) | 2022-08-29 | 2024-03-07 | Universität des Saarlandes | Alloy for producing bulk metallic glasses and shaped bodies therefrom |
| CN117568725A (en) * | 2023-11-20 | 2024-02-20 | 重庆师范大学 | Metallic glass-diamond composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3427154A (en) * | 1964-09-11 | 1969-02-11 | Ibm | Amorphous alloys and process therefor |
| US3856513A (en) * | 1972-12-26 | 1974-12-24 | Allied Chem | Novel amorphous metals and amorphous metal articles |
-
1975
- 1975-05-23 GB GB2281475A patent/GB1476589A/en not_active Expired
- 1975-06-24 JP JP7714675A patent/JPS5811500B2/en not_active Expired
- 1975-07-16 FR FR7522266A patent/FR2281434A1/en active Granted
- 1975-07-24 IT IT6892875A patent/IT1046075B/en active
- 1975-08-01 DE DE19752534379 patent/DE2534379C2/en not_active Expired
- 1975-08-06 CA CA75232901A patent/CA1048815A/en not_active Expired
-
1982
- 1982-10-29 JP JP19070082A patent/JPS6028899B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5811500B2 (en) | 1983-03-03 |
| JPS5120011A (en) | 1976-02-17 |
| JPS6028899B2 (en) | 1985-07-08 |
| FR2281434B1 (en) | 1978-10-13 |
| DE2534379C2 (en) | 1984-09-13 |
| GB1476589A (en) | 1977-06-16 |
| FR2281434A1 (en) | 1976-03-05 |
| IT1046075B (en) | 1980-06-30 |
| DE2534379A1 (en) | 1976-02-19 |
| JPS5891144A (en) | 1983-05-31 |
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