EP1632584A1 - Alliage amorphe à base de Zr et son utilisation - Google Patents

Alliage amorphe à base de Zr et son utilisation Download PDF

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EP1632584A1
EP1632584A1 EP04405550A EP04405550A EP1632584A1 EP 1632584 A1 EP1632584 A1 EP 1632584A1 EP 04405550 A EP04405550 A EP 04405550A EP 04405550 A EP04405550 A EP 04405550A EP 1632584 A1 EP1632584 A1 EP 1632584A1
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alloy
alloy according
alloys
temperature
component
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Jörg F. Löffler
Kaifeng Jin
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Eidgenoessische Technische Hochschule Zurich ETHZ
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Priority to EP04405550A priority Critical patent/EP1632584A1/fr
Priority to EP05775793A priority patent/EP1786942A1/fr
Priority to PCT/CH2005/000525 priority patent/WO2006026882A1/fr
Priority to US11/661,991 priority patent/US20080190521A1/en
Priority to JP2007529311A priority patent/JP5149005B2/ja
Priority to CN200580029743A priority patent/CN100580128C/zh
Publication of EP1632584A1 publication Critical patent/EP1632584A1/fr
Priority to JP2012085428A priority patent/JP5604470B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

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  • the present invention relates to an alloy with the features of the preamble of claim 1, to the use of such an alloy, and to articles manufactured from such an alloy, in particular implants such as endoprostheses.
  • a number of alloys may be brought into a glassy state, i.e., an amorphous, non-crystalline structure, by splat cooling at very high cooling rates, e.g., 10 6 K/s.
  • very high cooling rates e.g. 10 6 K/s.
  • most of these alloys cannot be cast into a bulk glassy structure at much lower cooling rates achievable with casting.
  • a "bulk metallic glass” is to be understood as an alloy which develops an at least partially amorphous structure when cooled from a temperature above the melting point to a temperature below the glass-transition temperature of the amorphous phase with a cooling rate of 1000 K/s or less, preferably with a cooling rate of 100 K/s or less. Cooling rates in this range are typically experienced in bulk casting operations.
  • Bulk metallic glasses generally have mechanical properties that are superior to their crystalline counterparts. Due to the absence of a dislocation mechanism for plastic deformation, they often have a high yield strength and elastic limit. Furthermore, many bulk metallic glasses show good fracture toughness, corrosion resistance, and fatigue characteristics. For an overview of the properties and areas of application of such materials see, for example, Johnson WL, MRS Bull. 24, 42 (1999) and Löffler JF, Intermetallics 11, 529 (2003). Reference is made explicitly to the disclosure of these documents and the references cited therein for teaching properties of glass-forming metallic alloys and methods for the determination of such properties. Commercial applications of bulk metallic glasses are described, e.g., in Buchanan O, MRS Bull. 27, 850 (2002).
  • an alloy which contains at least four components A, D, E and G.
  • a fifth component Z may be present.
  • the alloy has a bulk structure containing at least one amorphous phase, i.e., a volume fraction of at least 10%, preferably at least 50% of the alloy is amorphous.
  • a structure is considered to be fully amorphous if the material having this structure does not exhibit significant Bragg peaks in an X-ray diffraction pattern. Accordingly, the volume fraction of the amorphous phase in a mixed-phase material may be estimated by integrating the intensity of Bragg peaks and comparing with the intensity of non-Bragg features.
  • the amorphous phase can be obtained by cooling from a temperature above the melting point to a temperature below the glass-transition temperature of the amorphous phase with a cooling rate of 1000 K/s or less, i.e., preferably the alloy is a bulk metallic glass. More preferably, the amorphous phase can be obtained by cooling with a cooling rate of 100 K/s or less.
  • the alloy with at least one amorphous phase can be obtained in a shape with dimensions of at least 0.1 mm, preferably at least 0.5 mm, more preferred at least 1 mm in any spatial direction. This is not possible for alloys which adopt an amorphous structure only at cooling rates as achievable by splat cooling or melt spinning.
  • Component A consists of at least one element selected from the group consisting of Zr (zirconium), Hf (hafnium), Ti (titanium), Nb (niobium), La (lanthanum), Pd (palladium) and Pt (platinum).
  • the other components D, E, G and, optionally, Z are all different from each other and from component A.
  • Each of these components may consist of more than one element, as long as all elements of all components are different.
  • components D, E and G each consist of a single element.
  • the alloy composition follows an "80:20 scheme", i.e., the ratio of the combined atomic content of components A and D to the combined atomic content of components E and G is approximately 80 to 20, within a band of plus or minus 10, preferably a band of plus or minus 5, in particular a band of plus or minus 2.
  • the alloy composition is [(A x D 100-x ) a (E y G 100-y ) 100-a ] 100-b Z b , where x, y, a and b are independent numbers selected from zero and the positive real numbers and denote atomic percentages, with 70 ⁇ a ⁇ 90, preferably 75 ⁇ a ⁇ 85, more preferred 78 ⁇ a ⁇ 82.
  • each index indicates the number of atoms contributing to a formula unit of the alloy.
  • 58 atoms of Zr would be combined with 22 atoms of Cu, 8 atoms of Fe and 12 atoms of Al in order to arrive at one formula unit.
  • a number is an "atomic percentage" this means that the number, when divided by 100, indicates the stoichiometry in the sense as it is usually understood in chemistry.
  • Component A is the main component of the alloy, in the sense that x ⁇ 50.
  • x ⁇ 95 and more preferably x ⁇ 90 the content of component G relative to component E is not too small, preferably y ⁇ 5 , more preferred y ⁇ 10.
  • the content should not be too large.
  • a fifth component Z is present at all, then it is present in a comparatively small proportion only.
  • numbers, 0 ⁇ b ⁇ 6 preferably 0 ⁇ b ⁇ 4 , more preferably 0 ⁇ b ⁇ 2.
  • the numbers x, y, a and b are generally independent of each other.
  • the alloy is substantially free of nickel.
  • substantially free of nickel means that the total nickel content of the alloy is less than 1 atomic percent, preferably less than 0.1 atomic percent. It may even be required that the nickel content is below 10 atomic ppm, e.g., in medical applications.
  • none of the components A, D, E, G or Z should comprise nickel.
  • components A and E are miscible in a wide composition and temperature range.
  • the term "wide composition and temperature range” is to be understood as a range extending over a temperature range of at least 600 K and over a range of compositions spanning at least 60 at.% of either component in the liquid state and below the liquidus temperature in the A-E phase diagram.
  • a wide composition range would, e.g., be the range from 20 at.% to 80 at.% of component A in the binary mixture A-E.
  • components A and E are capable of forming a deep eutectic composition in the absence of other components.
  • the term "capable of forming a deep eutectic composition” is to be understood as meaning that, if A and E are mixed in the melt in the absence of other components, there is a composition for which A and E are miscible down to the liquidus temperature, and the liquidus temperature of the mixture for that composition has a local minimum as a function of composition. In other words, when varying the composition in a small vicinity of a deep eutectic, the liquidus temperature is higher than at the composition of the deep eutectic itself.
  • the liquidus temperature of the binary mixture at the deep eutectic will additionally be lower than the melting point of each of the components taken alone.
  • T m (Au) 1337 K
  • T m (Si) 1687 K
  • the components are chosen such that a deep eutectic composition of the A-E mixture occurs at a composition A a ,E 100-a' with 70 ⁇ a' ⁇ 90, preferably 75 ⁇ a' ⁇ 85.
  • the number a is preferably chosen such that the absolute value of the difference between a and a' is smaller or equal to 10 (i.e.,
  • components A and D are miscible over a wide temperature and composition range. More preferably, they are capable of forming a deep eutectic composition when mixed in a binary mixture. If components A and D form a deep eutectic composition at A x' D 100-x' , then x is preferably chosen such that
  • component G is miscible with component E over a wide temperature and composition range, in particular if E is at least one element selected from the group consisting of the transition metals, in particular the group consisting of Fe and Co. It is then preferred that G is capable of forming a deep eutectic composition with component A.
  • components G and E are capable of forming a deep eutectic composition at E y ,G 100-y' .
  • y is preferably chosen such that
  • a and G are preferably capable of forming a deep eutectic composition.
  • the atomic Goldschmidt radius of each element in component A is relatively large, at least 0.137 nm, preferably at least 0.147 nm, more preferred at least 0.159 nm.
  • the atomic Goldschmidt radius of each element in component A is at least 0.159 nm, then preferably 70 ⁇ a ⁇ 90, if this radius is at least 0.147 nm, then preferably 75 ⁇ a ⁇ 85, and if this radius is at least 0.137 nm, then preferably 78 ⁇ a ⁇ 82.
  • the components A, D, E and G may have similar atomic radii and atomic properties. However, it is preferred that the atomic radius of each element in component E is smaller than the atomic radius of each element in component A.
  • the atomic (Goldschmidt) radii of the elements can be found tabulated in standard textbooks or in the 2004 Goodfellow Catalog, available from Goodfellow Inc., Huntingdon, U.K. In particular, for selected elements, reference is made to Table 1 below.
  • component D is preferably at least one element selected from the group consisting of Cu (copper), Be (beryllium), Ag (silver) and Au (gold).
  • component A is at least one element selected from the group consisting of La (lanthanum), Pd (palladium) and Pt (platinum)
  • component D is preferably Cu (copper).
  • A is at least one element selected from the group consisting of Zr (zirconium), Hf (hafnium) and Ti (titanium)
  • D is preferably Cu (copper) or Be (beryllium). Both copper and beryllium have deep eutectics with Zr, Hf and Ti.
  • component E is preferably at least one metal selected from the group consisting of the transition metals except Ni (nickel); particularly Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Zn (zinc), Y (yttrium), Mo (molybdenum), Ta (tantalum), and W (tungsten).
  • a transition metal is defined as any of the thirty chemical elements with atomic number 21 through 30, 39 through 48, and 71 through 80. These metals are preferred because of their tendency to form deep eutectics with component A and because of their specific electronic properties.
  • component E is preferably at least one metal selected from Fe (iron) and Co (cobalt). These metals have empirically been found to be preferred.
  • Component G is preferably at least one element selected from the group consisting of Al (aluminum), Zr (zirconium), P (phosphorus), C (carbon), Ga (gallium), In (indium) and the metalloids, particularly B (boron), Si (silicon), and Ge (germanium).
  • the known metalloids are B (boron), Si (silicon), Ge (germanium), As (arsenic), Sb (antimony), Te (tellurium), and Po (polonium). It is believed that the specific electronic properties of these elements favorably influence the glass-forming ability.
  • the elements B, P, C, and Si have particularly small atomic sizes ( ⁇ 0.117 nm), which contributes to a large size difference between the components A and G.
  • component G is preferably selected from the group consisting of Al (aluminum), Zr (zirconium), P (phosphorus), B (boron), Si (silicon) and C (carbon). More preferred, if component E is Fe (iron), then component G is Al (aluminum). Then y is advantageously chosen to be in the range from about 30 to about 50, in particular approximately 40.
  • component E is Co (cobalt)
  • component G is preferably at least one element selected from the group consisting of Zr (zirconium), Al (aluminum), B (boron), Si (silicon), Ge (germanium), Ga (gallium) and In (indium).
  • component A is Zr (zirconium) or a mixture of Zr (zirconium) with either Hf (hafnium) or Ti (titanium) or both wherein at least 80 atomic percent of component A is Zr (zirconium). It is then preferred that component D is Cu (copper). It has been found empirically that this combination leads to alloys with superior glass-forming ability.
  • x is chosen between 62 and 83 (i.e., 62 ⁇ x ⁇ 83), preferably 68 ⁇ x ⁇ 77 , in particular that x is approximately 72.5.
  • component A is Zr and component D is Cu, it is further preferred that component E is Fe (iron) and component G is Al (aluminum).
  • y is advantageously chosen to be in the range from about 30 to about 50, in particular approximately 40. Alloys of this composition, specifically, the alloy compositions in the vicinity of Zr 58 Cu 22 Fe 8 Al 12 , have been found by the inventors to belong to the best glass formers known to date.
  • component Z is preferably at least one element selected from the group consisting of Ti, Nb, Hf.
  • component Z may preferably be at least one element selected from the group consisting of the transition metals, or component Z may preferably be at least one element selected from the group consisting of Be (beryllium), Y (yttrium), Pd (palladium), Ag (silver), Pt (platinum), and Sn (tin).
  • component Z is preferably capable of forming a deep eutectic composition with component A.
  • the alloy may have a structure comprising at least one amorphous phase and at least one crystalline phase.
  • the volume fraction of the amorphous phase preferably is at least 10%.
  • the amorphous and crystalline phases should not be macroscopically separated.
  • Such a structure can be generated by different means.
  • a composite comprising crystals embedded in an amorphous matrix is produced by subjecting the alloy to heat treatment at a temperature above the glass transition temperature. For details, see the description of the preferred embodiments below.
  • the alloy is subjected to electric currents, as described, e.g., in (Holland TB, Löffler JF, Mu-nir ZA, J. Appl. Phys.
  • the alloy composition in the melt is chosen to be initially outside the glass-forming region. During cooling, crystals start forming in the melt. This alters the composition of the mixture remaining in the melt, which is shifted into the glass-forming region. Upon further cooling, a glassy matrix with embedded crystals is formed. For details, see (Hays CC, Kim CP, Johnson WL, Phys Rev. Lett. 84, 2901 (2000)). In yet another approach, development of crystals in the amorphous matrix is fostered by a suitable choice of the fifth component Z.
  • Suitable components Z are preferably at least one element selected from the group consisting of Ti, Nb, Ta, or at least one element selected from the group consisting of the transition metals, or at least one element selected from the group consisting of Be and Pd.
  • Suitable components Z are preferably at least one element selected from the group consisting of Ti, Nb, Ta, or at least one element selected from the group consisting of the transition metals, or at least one element selected from the group consisting of Be and Pd.
  • the present invention is further directed at a method of manufacture of the inventive alloys.
  • the method comprises
  • the inventive alloys may be produced by mechanical alloying, as described, e.g., in (Eckert J, Mater. Sci. Eng. A 226-228, 364 (1997): Mechanical alloying of highly processable glassy alloys).
  • Mechanical alloying means mechanical processing of the alloy or its constituents in the solid state, without passing through the liquid state.
  • mechanical alloying e.g., a crystalline powder
  • an amorphous metallic alloy may be obtained.
  • Suitable mechanical alloying methods include, but are not restricted to, ball milling.
  • explicit reference is made to the teachings of the above-mentioned Eckert paper.
  • the method may additionally comprise a step of processing the alloy above the glass transition temperature, e.g., for obtaining a mixed-phase material.
  • the method may comprise a step of heat-treating the solidified material for a few minutes up to 15 hours at a temperature below the first crystallization temperature or for a few seconds up to 2 hours at a temperature above the first crystallization temperature.
  • the first crystallization temperature is the temperature of the first exothermic feature in a DTA scan of the amorphous alloy when the temperature is raised from the glass transition temperature. Heat treatment at relatively low temperatures results in slow kinetics, which is believed to lead to the formation of small crystals. For details, see the description of the preferred embodiments below.
  • the alloy may be subjected to a microstructuring process as described, e.g., in (Kundig AA, Cucinelli M, Uggowitzer PJ, Dommann A, Microelectr. Eng. 67, 405 (2003): Preparation of high aspect ratio surface microstructures out of a Zr-based bulk metallic glass) or in the patent application PCT/CH 2004/000401.
  • Microstructuring may be achieved by casting the liquid alloy into a mold having itself a microstructured surface.
  • Kundig et al. paper and to PCT/CH 2004/000401.
  • an already solidified alloy is brought into a superplastic state, i.e, into a state in which it can be easily shaped, by heating the alloy to a temperature above the glass-transition temperature, and is pressed onto a microstructured matrix.
  • the microstructured mold resp. matrix is a silicon wafer which has been structured by etching, as it is well known in the art.
  • the liquid alloy is drawn into a system of capillaries by the capillary effect and rapidly solidified within the capillaries. For details, reference is made to the teachings of the application PCT/CH 2004/000401.
  • the invention is also directed at the use of an inventive alloy for the manufacture of an article destined to be brought into contact with the human or animal body.
  • the invention is directed at the use of such an alloy for the manufacture of a surgical instrument, a jewelry item, in particular a watch case, or a prosthesis, in particular an endoprosthesis, specifically, a so-called stent.
  • a stent is an endoprosthesis for insertion into a blood vessel, lining the inner surface of the vessel. Stents are used in particular for ensuring sufficient blood flow through the vessel, or for stabilizing the blood vessel to prevent aneurisms.
  • inventive alloys are in the field of os-teosynthesis, e.g., hip implants, artificial knees, etc.
  • inventive alloys are in the field of os-teosynthesis, e.g., hip implants, artificial knees, etc.
  • the present invention is also directed at an endoprosthesis, in particular a stent, manufactured from an inventive alloy.
  • inventive alloys are particularly suited for such biomedical applications due to their good biocompatibility, high strength and high elasticity.
  • inventive alloys of general composition Zr-Cu-Fe-Al are well suited for these purposes.
  • inventive alloys Before describing specific examples of inventive alloys and their characterization, the concept which led to the development of the inventive alloys shall be described and exemplified.
  • nickel improves the glass-forming abilities of an alloy, making nickel an essential component of many quaternary bulk glass-forming alloys, and especially of Zr-based alloys, it has been found by the inventors that nickel can be dispensed with by following the principles of the present invention, while still alloys with excellent glass-forming abilities are obtained.
  • Zr and Cu have eutectic compositions, one of which occurs at 72.5% Zr, as illustrated in Fig. 2.
  • This diagram shows, again in a highly schematic fashion, the liquidus line. At various compositions between 38.2 at.% and 72.5 at.%, several other eutectics are expected.
  • the fourth component in the above-mentioned general composition is Al.
  • Fig. 3 shows, again in a highly schematic fashion, part of the phase diagram of a binary Al-Fe alloy. Several solid-solid transitions have been included in this diagram. In particular, a high-temperature phase, the so-called ⁇ -phase 301, is present around the composition Al 6 Fe 4 . This phase prevents a deep eutectic to be present at around 60 at.% in the Al-Fe phase diagram, which would otherwise be expected by extrapolation, as indicated by the dotted line in Fig. 3.
  • the concept is believed to be generally applicable and not to be restricted to the particular Zr-Cu-Fe-Al system described above.
  • the same considerations may be applied to alloys which are based on Ti, Hf, Nb, La, Pd or Pt as a main component.
  • other elements having a deep eutectic with the main component may be employed.
  • Particularly good candidates are Be, Ag and Au.
  • the Fe component may be replaced by one or more of the transition metals except Ni, e.g. by Co.
  • the Al component may be replaced by, e.g., Zr or one or more of the metalloids.
  • Ingots were prepared by arc melting the constituents (purity > 99.9%) in a titanium-gettered argon atmosphere (99.9999% purity). Using an induction-heating coil, the ingots were remelted in a quartz tube (vacuum ⁇ 10 -5 mbar) and injection cast into a copper mold with high-purity argon. Samples were cast into plates with a thickness of 0.5 mm, width of 5 mm and length of 10 mm.
  • XRD X-ray diffraction
  • SANS small-angle neutron scattering
  • DTA differential thermal analysis
  • XRD was performed with a Scintag XDS-2000 X-ray diffractometer, using a collimated monochromatic Cu K ⁇ x-ray source.
  • the Ni-bearing alloy Zr 65 Al 7.5 Ni 10 Cu 17.5 was also investigated by DTA. This result is also shown in Fig. 6 for comparison.
  • Table 2 gives the characteristic values extracted from DTA scans like those of Figs. 6 and 7.
  • the glass transition temperatures T g were extracted from the onset of the endothermic events in Fig. 6 (arrows pointing up) and the first crystallization temperatures T x1 were obtained from the onset of the exothermic peaks (arrows pointing down).
  • the onset of melting T m and the offset of melting T 1 were obtained from scans like that in Fig. 7.
  • Table 2 lists the ratios of T g/ T m also, since in many publications this ratio has been used as the reduced glass transition temperature.
  • the value of T g / T m is 0.59 to 0.62 for the new Ni-free alloys and thus significantly larger than that of Zr 65 Al 7.5 Ni 10 Cu 17.5 . Table 2.
  • Fig. 9 shows X-ray diffraction patterns of Zr 58 Cu 22 Fe 8 Al 12 cast to cylindrical rods of diameters 5, 7 and 8 mm, and to a plate of 1 mm thickness (inset). No Bragg peaks are apparent either in the 5 mm rod sample or in the 1 mm plate, while only very weak Bragg peaks seem to arise in the 7 mm rod sample. In contrast, a clear crystalline component is present in the 8 mm rod sample, as apparent from the strong Bragg peaks from that sample.
  • the XRD scans were performed on 0.5 mm thick plates cut perpendicularly to the longitudinal axis of the cone. The average diameter of the corresponding plates is given in the figure.
  • the XRD patterns of the plates with diameters of 5 mm or less show typical amorphous structures, while the plate with 6 mm diameter appears to show some Bragg peaks indicating a small volume fraction of crystals in the amorphous matrix. This is perfectly consistent with the findings for rods with uniform diameter.
  • These experimental results agree well with the Turnbull theory (D. Turnbull, Contemp. Phys. 10, 473 (1969), F. Spa-epen and D. Turnbull, Proc. Sec. Int. Conf. on Rapidly Quenched Metals (Cam-bridge, Mass.: M.I.T. Press, 1976), pp. 205-229), which predicts that the best glass-forming ability is obtained for the alloy with the highest ratio of Tg / T I (see Table 2).
  • the composition of the material can be varied within rather broad limits without losing the good glass-forming properties. Specifically, it may be expected that a variation in the composition with respect to the other constituent elements, in particular a moderate variation of the numbers a and y, will not alter the glass-forming ability dramatically. Furthermore, it is expected that addition of a small amount of an additional component will not negatively affect the glass-forming ability or even possibly improve the glass-forming ability of the inventive materials, while possibly improving certain desired properties.
  • Samples with a mixed-phase structure were prepared as follows: Fully amorphous samples of Zr 58 Cu 22 Fe 8 Al 12 were prepared as in Example 1. The samples were subjected to heat treatment (annealing) at various temperatures for 12 hours. XRD patterns and DTA scans were recorded for the heat-treated samples. Fig. 15 shows XRD patterns of the samples in the as-prepared state (bottom trace) and after annealing. The XRD patterns show typical amorphous structures up to an annealing temperature of 683 K. At higher annealing temperatures, however, clear Bragg peaks arising from an icosahedral phase (I.P.) can be observed. At still higher temperatures, peaks which are typical for a Zr 2 Fe structure are observed. Fig.
  • FIG. 16 shows the XRD pattern of the sample annealed at 708 K for 12 hours in more detail.
  • the indexing indicates the presence of an icosahedral phase with a lattice constant of 0.476 nm.
  • Fig. 17 shows DTA scans of the same samples as in Fig. 15, which are consistent with the development of a structure with both glassy and crystalline components.
  • the laboratory glass transition temperature is to be understood as the glass transition temperature as determined by DSC (differential scanning calorimetry) with a typical heating rate of 20 K/min. Higher annealing temperatures often lead to the precipitation of larger crystals; for example in the range of 0.1 - 20 ⁇ m.
  • Such mixed-phase materials exhibit somewhat different mechanical properties than a fully glassy material.
  • ductility is often improved, which can be rationalized by the fact that shear bands which develop as a result of shear forces during forming and which might lead to breaking of the material are disrupted by the crystals. These properties may be particularly beneficial in applications where the material must be shaped or deformed during manufacture of the end product.
  • compositions of the following Tables proved to be at least partially amorphous when cast to a plate with thickness of 1 mm (Table 4), 0.5 mm (table 5), or 0.2 mm (Table 6): Table 4: Alloys having a partially or fully amorphous structure when cast to a thickness of 1 mm.
  • Table 7 Comparative listing of other alloys with a partially or fully amorphous structure when cast to a thickness of 0.2 mm.
  • this list shows that also ternary, nickel-free alloys can be reasonably good glass-formers, especially if composed according to the "80:20 scheme".
  • the list shows that ternary alloys of composition (Zr x D 100-x ) a Fe 100-a , where the number a is in the range from about 70 to about 90, in particular approximately 80, are good glass formers.
  • D is advantageously Cu, Nb, Al or Sn.
  • the alloys in Table 8 have also been prepared and were found to be fully amorphous when subjected to splat cooling to a thickness of 20 micrometers at high cooling rates of approximately 10 6 K/s. These alloys may be regarded as candidate materials for bulk metallic glasses, while casting experiments will be necessary to verify which of these are indeed bulk metallic glasses.
  • Table 8 Alloys having a fully amorphous structure when splat-cooled. All numbers are atomic percentages.
  • Table 9 Ternary alloys having a fully amorphous structure when splat-cooled.

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EP04405550A 2004-09-06 2004-09-06 Alliage amorphe à base de Zr et son utilisation Withdrawn EP1632584A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP04405550A EP1632584A1 (fr) 2004-09-06 2004-09-06 Alliage amorphe à base de Zr et son utilisation
EP05775793A EP1786942A1 (fr) 2004-09-06 2005-09-05 Alliage amorphe à base de zr et utilisation
PCT/CH2005/000525 WO2006026882A1 (fr) 2004-09-06 2005-09-05 Alliages amorphes sur la base de zr et leur utilisation
US11/661,991 US20080190521A1 (en) 2004-09-06 2005-09-05 Amorphous Alloys on the Base of Zr and their Use
JP2007529311A JP5149005B2 (ja) 2004-09-06 2005-09-05 ジルコニウム系非晶質合金及びその使用
CN200580029743A CN100580128C (zh) 2004-09-06 2005-09-05 以zr为基础的非晶合金及其用途
JP2012085428A JP5604470B2 (ja) 2004-09-06 2012-04-04 ジルコニウム系非晶質合金及びその使用

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US8057530B2 (en) 2006-06-30 2011-11-15 Tyco Healthcare Group Lp Medical devices with amorphous metals, and methods therefor
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US8852264B2 (en) 2000-03-24 2014-10-07 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stent
US9566147B2 (en) 2010-11-17 2017-02-14 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stents comprising cobalt-based alloys containing one or more platinum group metals, refractory metals, or combinations thereof
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Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US20150047463A1 (en) 2012-06-26 2015-02-19 California Institute Of Technology Systems and methods for implementing bulk metallic glass-based macroscale gears
WO2014030272A1 (fr) * 2012-08-23 2014-02-27 国立大学法人東北大学 Élément dentaire
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EP2881488B1 (fr) * 2013-12-06 2017-04-19 The Swatch Group Research and Development Ltd. Alliage amorphe massif à base de zirconium sans béryllium
KR20160145668A (ko) * 2014-04-09 2016-12-20 캘리포니아 인스티튜트 오브 테크놀로지 벌크 비정질 금속계 스트레인 웨이브 기어들 및 스트레인 웨이브 기어 컴포넌트들을 구현하기 위한 시스템들 및 방법들
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CN115449723A (zh) * 2022-09-21 2022-12-09 盘星新型合金材料(常州)有限公司 同时含有Sn和Fe的大尺寸锆基非晶合金及其制备方法
CN115537685A (zh) * 2022-10-10 2022-12-30 江苏恩夏科技发展有限公司 一种非晶军用装甲防护材料

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0433670A1 (fr) * 1989-11-17 1991-06-26 Tsuyoshi Masumoto Alliages amorphes, présentant une usinabilité améliorée
US5803996A (en) * 1995-01-25 1998-09-08 Research Development Corporation Of Japan Rod-shaped or tubular amorphous Zr alloy made by die casting and method for manufacturing said amorphous Zr alloy
US20020162605A1 (en) * 2001-03-05 2002-11-07 Horton Joseph A. Bulk metallic glass medical instruments, implants, and methods of using same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3359750B2 (ja) * 1994-09-09 2002-12-24 明久 井上 ジルコニウム非晶質合金棒材の製造方法及び金型で鋳造成型されたジルコニウム非晶質合金
US5772803A (en) * 1996-08-26 1998-06-30 Amorphous Technologies International Torsionally reacting spring made of a bulk-solidifying amorphous metallic alloy
JP4202002B2 (ja) * 2001-05-10 2008-12-24 独立行政法人科学技術振興機構 高降伏応力Ｚｒ系非晶質合金
JP2004089580A (ja) * 2002-09-03 2004-03-25 Kozo Nakamura 生体材料部材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0433670A1 (fr) * 1989-11-17 1991-06-26 Tsuyoshi Masumoto Alliages amorphes, présentant une usinabilité améliorée
US5803996A (en) * 1995-01-25 1998-09-08 Research Development Corporation Of Japan Rod-shaped or tubular amorphous Zr alloy made by die casting and method for manufacturing said amorphous Zr alloy
US20020162605A1 (en) * 2001-03-05 2002-11-07 Horton Joseph A. Bulk metallic glass medical instruments, implants, and methods of using same
US20030111142A1 (en) * 2001-03-05 2003-06-19 Horton Joseph A. Bulk metallic glass medical instruments, implants, and methods of using same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LÖFFLER, J.F.: "Bulk metallic glasses", INTERMETALLICS, vol. 11, 2003, pages 529 - 540, XP002314395 *

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* Cited by examiner, † Cited by third party
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US8852264B2 (en) 2000-03-24 2014-10-07 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stent
CN100494464C (zh) * 2006-03-17 2009-06-03 浙江理工大学 塑性Zr-Cu-Al-Ag系大块非晶合金
US8057530B2 (en) 2006-06-30 2011-11-15 Tyco Healthcare Group Lp Medical devices with amorphous metals, and methods therefor
EP2460543A1 (fr) * 2006-06-30 2012-06-06 Tyco Healthcare Group LP Dispositifs médicaux avec des métaux amorphes et procédés correspondants
EP2460544A1 (fr) * 2006-06-30 2012-06-06 Tyco Healthcare Group LP Dispositifs médicaux avec des métaux amorphes et procédés correspondants
WO2011159596A1 (fr) * 2010-06-14 2011-12-22 Crucible Intellectual Property, Llc Alliage amorphe contenant de l'étain
US9869010B2 (en) 2010-06-14 2018-01-16 Crucible Intellectual Property, Llc Tin-containing amorphous alloy
EP2565289A4 (fr) * 2010-07-29 2017-05-17 Shenzhen BYD Auto R&D Company Limited Valve hydraulique, ensemble valve hydraulique et procédé de commande de valve hydraulique
US9566147B2 (en) 2010-11-17 2017-02-14 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stents comprising cobalt-based alloys containing one or more platinum group metals, refractory metals, or combinations thereof
CN103209718A (zh) * 2010-11-17 2013-07-17 艾博特心血管***公司 包含含有一种或更多种铂族金属、难熔金属或其组合之钴基合金的不透射线的管腔内支架
WO2012068358A1 (fr) * 2010-11-17 2012-05-24 Abbott Cardiovascular Systems, Inc. Endoprothèses intraluminales radio-opaques comportant des alliages à base de cobalt contenant un ou plusieurs métaux du groupe du platine, des métaux réfractaires ou des combinaisons de ceux-ci
US10441445B2 (en) 2010-11-17 2019-10-15 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stents comprising cobalt-based alloys containing one or more platinum group metals, refractory metals, or combinations thereof
US11298251B2 (en) 2010-11-17 2022-04-12 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stents comprising cobalt-based alloys with primarily single-phase supersaturated tungsten content
US11779477B2 (en) 2010-11-17 2023-10-10 Abbott Cardiovascular Systems, Inc. Radiopaque intraluminal stents
US11806488B2 (en) 2011-06-29 2023-11-07 Abbott Cardiovascular Systems, Inc. Medical device including a solderable linear elastic nickel-titanium distal end section and methods of preparation therefor
CN107829050A (zh) * 2017-11-08 2018-03-23 湖南理工学院 一种含铝的铜基块体非晶合金及其制备工艺
CN110079701A (zh) * 2019-05-05 2019-08-02 河北工业大学 一种高强度锆合金及其制备方法
CN116580795A (zh) * 2023-05-16 2023-08-11 燕山大学 一种基于熔化熵和金属间化合物的金属玻璃的成分设计方法
CN116580795B (zh) * 2023-05-16 2023-11-21 燕山大学 一种基于熔化熵和金属间化合物的金属玻璃的成分设计方法

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JP2012162805A (ja) 2012-08-30
CN101010440A (zh) 2007-08-01
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CN100580128C (zh) 2010-01-13
WO2006026882A1 (fr) 2006-03-16

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