# Patent

## Title
Thermoplastically processable amorphous metals and methods for processing same

## Abstract

High strength, thermoplastically processable (TPF) amorphous alloys composed of Beryllium and at least one ETM and at least one LTM, as well as methods of processing such alloys are provided. The TPF alloys of the invention demonstrate good glass forming ability, low viscosity in the supercooled liquid region (SCLR), a low processing temperature, and a long processing time at that temperature before crystallization.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
The current invention claims priority to U.S. Provisional Application No. 60/873,515, filed Dec. 7, 2006, U.S. Provisional Application No. 60/881,960, filed Jan. 23, 2007, and U.S. Provisional Application No. 60/923,221, filed Apr. 13, 2007, the disclosures of each of which are incorporated herein by reference.


STATEMENT OF FEDERAL RIGHTS
The U.S. Government has certain rights in this invention pursuant to Grant No. DMR0520565 awarded by the National Science Foundation.


FIELD OF THE INVENTION
The current invention is directed to high strength amorphous alloys that can be thermoplastically processed to make material parts and articles, and methods of thermoplastically processing such amorphous alloys.
BACKGROUND OF THE INVENTION
Over the last two decades metallic glasses (MGs) have received increasing attention because of their unique characteristics, such as high strength, high specific strength, large elastic strain limit, excellent wear and corrosion resistance, along with other remarkable engineering properties. (For further discussion see, e.g., A. L. Greer, Science 1995, 267, 1947; W. L. Johnson, MRS Bulletin 1999, 24, 42; A. Inoue, Acta Materialia 2000, 48, 279; D. H. Xu, G. Duan, and W. L. Johnson, Physical Review Letters 2004, 92, 245504; V. Ponnambalam, et al., Journal of Materials Research 2004, 19, 1320; and Z. P. Lu, C. T. Liu, J. R. Thompson, W. D. Porter, Physical Review Letters 2004, 92, 245503, the disclosures of which are incorporated herein by reference.) Because of the promise shown by these materials, researchers have designed a multitude of multi-component systems that form amorphous glassy alloys, among which Zr— (U.S. Pat. No. 5,288,344, referred to as Vit1 series of alloys, the disclosure of which is incorporate herein by reference) bulk metallic glasses (BMGs) have been utilized commercially to produce a variety of items, including, for example, sporting goods, electronic casings, and medical devices.
Most practical applications of MGs demand near-net-shaping process in manufacturing. However, conventional die casting, the common technique for net-shape processing of metals, requires fast cooling to bypass the crystallization of most MGs during solidification. This fast cooling requirement limits the ability to make pieces of large cross-section (i.e., limited by critical casting thickness), limits the ability to make parts with high aspect ratios (i.e., with large thin walls), and limits the ability to make high quality casts or to manufacture structures with complex geometries. Nevertheless, the properties of these MGs, including their high glass forming ability, good processability, large supercooled liquid region (SCLR), and a viscosity that varies continuously and predictably in the supercooled liquid region continues to hold out the promise that they could be processed thermoplastically if suitable candidate materials can be identified.
The unique advantages of injection molding, blow molding, micro-replication, and other thermoplastic technologies are largely responsible for the widespread uses of plastics such as polyethylene, polyurethane, PVC, etc., in a broad range of engineering applications. Powder Injection Molding (PIM) of metals represents an effort to apply similar processing to metals, but requires blending of the powder with a plastic binder to achieve net shape forming and subsequent sintering of the powder. Given suitable materials, thermoplastic forming (TPF) would be the method of choice for manufacturing of metallic glass components because TPF decouples the forming and cooling steps by processing glassy material at temperatures above the glass transition temperature (Tg) and below the crystallization temperature (Tx) followed by cooling to ambient temperature. (See, e.g., J. Schroers, JOM 2005, 57, 35; and J. Schroers, N. Paton, Advanced Materials & Processes 2006, 164, 61, the disclosures of which are incorporated herein by reference.)
Thermoplastic forming (TPF) of MGs is a net-shaping processing method taking place in the supercooled liquid region of such materials, which is the temperature region in which the amorphous material first relaxes into a viscous metastable liquid before crystallization. Operating in this supercooled liquid region, TPF decouples the fast cooling and forming of MG parts and allows for the replication of small features and thin sections of metals with high aspect ratios. TPF has several advantages over conventional die casting, including smaller solidification shrinkage, less porosity of the final product, more flexibility on possible product sizes, a robust process that does not sacrifice the mechanical properties of the material, and no cooling rate constraints on the thickness of parts that can be rendered amorphous (critical casting thickness).
From a processing point of view, MG alloys with an extremely large supercooled liquid region (excellent thermal stability against crystallization), which can provide lower processing viscosities and exhibit smaller flow stress, would be desirable for use in conjunction with a TPF process. In addition, excellent glass forming ability and low glass transition temperature (Tg) are also preferred to thermoplastically process MGs. Unfortunately, among the published metallic glasses, only the expensive Pt-, and Pd-based glasses have shown good thermoplastic formability. (See, e.g., J. Schroers, W. L. Johnson, Applied Physics Letters 2004, 84, 3666; G. J. Fan, et al., Applied Physics Letters 2004, 84, 487; and J. P. Chu, et al., Applied Physics Letters 2007, 90, 034101, the disclosures of which are incorporated herein by reference.) Zr-based metallic glasses, especially the Vitreloy series, are much less expensive than Pt- and Pd-based alloys, have exceptional glass forming ability, but they are usually strong liquids (the drop of viscosity with temperature is not steep) and low processing viscosities are unattainable in the supercooled liquid region (SCLR) between Tg and Tx. (See, e.g., A. Masuhr, et al., Physical Review Letters 1999, 82, 2290; R. Busch, W. L. Johnson, Applied Physics Letters 1998, 72, 2695; F. Spaepen, Acta Metallurgica 1977, 25, 407; and J. Lu, G. Ravichandran, W. L. Johnson, Acta Materialia 2003, 51, 3429, the disclosures of which are incorporated herein by reference.) One exception to this general rule is Vit1b (Zr44Ti11Cu10Ni10Be25); however, even this allow only provides accessible viscosities of  ̃10^Pa-s, substantially higher than the viscosities needed to access most thermoplastic forming techniques. (See, Schroers, J., et al. Scripta Materialia, 2007, 57, 341-344.1
Accordingly, a need exists for a new family of inexpensive MGs that can be incorporated into a thermoplastic processing application.
SUMMARY OF THE INVENTION
The current invention is directed to a new class of amorphous alloys that can be thermoplastically processed to make material parts and articles, and methods of thermoplastically processing such amorphous alloys.
The current invention is directed to BMG alloy compositions comprising beryllium, at least one ETM, and at least one LTM, and to methods of forming such BMG alloy compositions where at a heating rate of 20 K/min the alloy has a ΔT of at least 135 K and a viscosity that falls below a value of less than about 105 Pa-s. In one such an embodiment the composition is in accordance with the equation:

(ZrxTi(1-x))a1ETMa2CUb1LTMb2Bec,

where x is an atomic fraction and a1, a2, b1, b2, and c are atomic percentages, and where (a1+a2) falls within the range of 60 to 80% and x is in the range of 0.05 to 0.95; and

In one embodiment, the invention is directed to quaternary BMG compositions having a base composition of Be—Ti—Zr—Cu. In such an embodiment up to 15% of the Ti or Zr can be substituted with another element. In one such embodiment the additional element is an early transition metal. Also, in such an embodiment, Cu can be substituted with another late transition metal, such as Fe or Co.
In another embodiment of the invention the ternary BMGs in accordance with the current invention readily form an amorphous phase upon cooling from the melt at a rate less than 103 K/s.
The above-mentioned and other features of this invention and the manner of obtaining and using them will become more apparent, and will be best understood, by reference to the following description, taken in conjunction with the accompanying drawings. The drawings depict only typical embodiments of the invention and do not therefore limit its scope.



BRIEF DESCRIPTION OF THE DRAWINGS
These and other features and advantages of the present invention will be better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings wherein:
FIG. 1a provides an overlay of a DSC scan and a viscosity curve of the supercooled liquid region of a conventional amorphous alloy;
FIG. 1b provides a data graph comparing the viscosities of a conventional amorphous alloy and an exemplary alloy in accordance with the current invention.
FIG. 2 provides a schematic TTT diagram showing two possible thermoplastic processing routes (Johnson) versus the injection molding processing route (TPF) described in the current invention;
FIG. 3 provides a schematic diagram of a cavitated pore formed during conventional die casting of a bulk part;
FIG. 4 provides a schematic TTT diagram showing the injection molding processing route described in the current invention;
FIG. 5 provides a schematic diagram of an injection molding apparatus in accordance with an exemplary embodiment of the current invention;
FIG. 6 provides DSC scans of three typical bulk metallic glasses with excellent glass forming ability and extremely high thermal stability in accordance with the current invention;
FIG. 7 provides a comparison graph of the temperature dependence of the equilibrium viscosity of several metallic glass forming liquids;
FIG. 8 provides a comparison of TTT diagrams for several amorphous alloys;
FIG. 9a to 9d provide photographs of a demonstration of the thermoplastic processability of an exemplary metallic glass in accordance with the current invention;
FIG. 10 provides photographs of exemplary injection molded parts in accordance with one embodiment of the thermoplastic processing methodology of the current invention;
FIG. 11 provides a comparison data graph of the rupture modulus of a die cast piece versus a piece molded in accordance with the injection molding process of the current invention; and
FIG. 12 provides a comparison data graph of the Weibull modulus of a die cast piece versus a piece molded in accordance with the injection molding process of the current invention.



DETAILED DESCRIPTION OF THE INVENTION
In general terms, the current invention is directed to producing a new class of high strength, thermoplastically processable amorphous alloys, which in the broadest terms are composed of Beryllium and at least one ETM and LTM. The materials of the current invention possess a unique combination of properties including, low density, viscosities in the thermoplastic zone (at least one order of magnitude lower than that of the commercialized Zr-based alloys and lower also to the viscosity of Pd-based metallic glass and approaching the viscosities attainable in polymer glasses), high thermal stability (up to 165 K), low Tg (about 300° C.), and good glass forming ability (critical casting thickness at least 15 mm). As a result of these unique property combinations, these alloys demonstrate good thermoplastic processability, and combined with their excellent mechanical properties, these alloys are appropriate for use in a number of applications, including microelectromechanical systems, nano- and microtechnology, and medical and optical applications. Moreover, the large supercooled liquid region offered by these unique alloys in the current invention enables Newtonian flow conditions at strain rates higher than those of a conventional metallic glass with a smaller supercooled liquid region. This capability can be utilized for more efficient wire/fiber/plate/sheet drawing process.
DEFINITIONS
Early Transition Metal (ETM): For purposes of this invention, early transition metals are defined as elements from Groups 3, 4, 5 and 6 of the periodic table, including the lanthanide and actinide series. The previous IUPAC notation for these groups was IIIA, IVA, VA and VIA.
Late Transition Metal (LTM): For purposes of this invention, late transition metals are defined as elements from Groups 7, 8, 9, 10 and 11 of the periodic table. The previous IUPAC notation was VIIA, VIIIA and IB.
Amorphous Alloys or Metallic Glasses (MGs): For purposes of this invention, metallic glasses are defined as materials which are formed by solidification of alloy melts by cooling the alloy to a temperature below its glass transition temperature before appreciable homogeneous nucleation and crystallization has occurred.
Thermoplastic Processing (TPF): For the purposes of this invention, thermoplastic processing/forming is defined as a processing technique for forming metallic glasses in which the metallic glass is held at a temperature in a thermoplastic zone, which is below Tnose (the temperature at which crystallization of the amorphous alloy occurs on the shortest time scale, which means that the resistance of crystallization is minimum) and above Tg (the glass transition temperature) during the shaping or molding step, followed by a quenching step where the item is cooled to the ambient temperature.
Extruding: For the purposes of this invention, extruding is defined as either to force, press, or push out; or to shape (as metal or plastic) by forcing through a die.
Injection molding: For the purposes of this invention, injection molding is defined as a method of forming articles (as of plastic) by heating the molding material to a temperature within the SCLR until it can flow and injecting it into a mold.
Discussion of TPF Alloys
As discussed previously, one of the major limitations faced in forming conventional amorphous alloys is the small processing window available before crystallization, and the relatively high viscosity of the material within that processing window. Forming processes for these materials are further complicated by the interrelation between the viscosity of the alloy and the temperature at which the alloy crystallizes. To demonstrate this FIG. 1a provides an overlay of a DSC scan and a viscosity curve for one of the best conventional amorphous alloy showing how viscosity drops in the supercooled liquid region until crystallization. As shown, for these materials the lowest viscosities are accessible close to Tx. (Note that in FIG. 1a the viscosity curve (inset) is aligned with the temperature scale from the DSC curve.) Unfortunately, in most amorphous alloys the supercooled region is such that the viscosity remains too high for most thermoplastic processing techniques at temperatures that allow the material to retain its amorphous character. For example, typically metallic glass viscosity  ̃10^7 Pa-s whereas polymers are injection molded at  ̃10^3 Pa-s. In contrast, the viscosity of an exemplary alloy of the current invention (Zr35Ti30Cu7.5Be27.5) when measured at a heating rate of 20 K/min is less than about 10^5 Pa-s, two orders of magnitude lower than conventional amorphous materials, as shown in FIG. 1b. 
The strain rate sensitivity for the Vitreoy alloys has been extensively studied (J. Lu, G. Ravichandran, W. L. Johnson, Acta Materialia 2003, 51, 3429, the disclosure of which are incorporated herein by reference). As is known from follow-up analysis of the same experimental data, higher thermal stability of the supercooled liquid can lead to a substantial increase of the strain rate limit for Newtonian flow. Specifically, it has been shown that if the supercooled liquid can remain stable at 135 K above the glass transition temperature, at least 5 orders of magnitude increase in the strain rate limit for Newtonian flow can be realized. (See, M. D. Demetriou, and W. L Johnson, Scripta Materialia, 2005, 52, 833, the disclosure of which are incorporated herein by reference.) Newtonian flow conditions are necessary and important for applications involving tensile loading, such as wire/fiber/plate/sheet drawing. Non-Newtonian flow gives rise to shear thinning that leads to necking and cessation of the process. Therefore, a high strain rate capability while maintaining Newtonian flow can enable a more efficient drawing process.
In general terms, the current invention is directed to producing high strength, thermoplastically processable (TPF) amorphous alloys which are composed of Beryllium and at least one ETM and at least one LTM. An alloy optimal for TPF would have good glass forming ability, low viscosity in the SCLR, a low processing temperature, and a long processing time at that temperature before crystallization. It has been found that Be-bearing Zr—Ti based quaternary metallic glasses having compositions that fall within the range of 60%<Zr+Ti<, 80% have Lower Tg, and increased SCLR in comparison with conventional bulk solidifying amorphous alloys such as the Vitreloy alloys (Zr+Ti=55%).
More specifically, the amorphous alloys of the current invention comprise Beryllium and at least one ETM and at least one LTM in accordance with the formula:

(ZrxTi(1-x))a1ETMa2Cub1LTMb2Bec,

where x is an atomic fraction and a1, a2, b1, b2, and c are atomic percentages, and where (a1+a2) falls within the range of 60 to 80%, x is in the range of 0.05 to 0.95. In addition, it is required that Ni make up no more than a fractional amount of the overall alloy composition, defined herein as less than 5% of the total alloy composition.

In a preferred embodiment of the invention, the alloy formulation may be expressed by the following formulation:

ZraTibCucBed,

and falls within one of the following sub-ranges where a+b+c+d equals 100%:

    
    
        where a+b>60% with d>15%
        where a≈b with d>15%; and
        where a≈5b with d>20%.
    
    


Although specific ranges of materials are provided above, it should be understood that variations and modifications to the proposed invention can exist with respect to the composition of amorphous alloys. For example other elements, excluding ETMs and LTMs, can be added to the alloys without significantly altering the base alloy properties. Such materials may include, for example, Sn, B, Si, Al, In, Ge, Ga, Pb, Bi, As and P. In addition, Cu can be substituted with other LTMs such as, for example, Co and Fe, but in any event the concentration of Ni in the alloy cannot exceed 5% of the total alloy composition.
Regardless of the specific compositional substitutions made, the two key distinguishing features of alloys made in accordance with the above formulations are that when heated at a rate of 20 K/min the alloys have supercooled liquid regions of at least 135 K, and that at a heating rate of 20 K/min the alloys have processing viscosities in the supercooled liquid region of less than around 10^5 Pa-s (unprecedentedly low for a metallic glass forming system). Accordingly, the alloys of the current invention exhibit “benchmark” characteristics for thermoplastic processing. Table 1 below, provides a listing of exemplary alloy formulations in accordance with the above ranges along with thermal properties for those alloys.







TABLE 1







Summary of BMG forming alloys investigated


in the current invention.












Materials
Tg
Tx
Tl
ΔT
Trg















Zr35Ti30Be30Cu5
574.9
725.3
1114.4
150.4
0.516


Zr35Ti30Be27.5Cu7.5
574.6
739.7
1070.7
165.1
0.537


Zr35Ti30Be26.75Cu8.25
578.2
737.2
1044.2
159
0.554


Zr54Ti11Be22.5Cu12.5
581
721
1035
140
0.561


Zr54Ti11Be17.5Cu17.5
584
722
1074
138
0.544


Zr51Ti9Be27.5Cu12.5
595
731
1042
136
0.571


Zr51Ti9Be25Cu15
592
730
1047
138
0.565


Zr40Ti25Be29Cu6
579.7
728.1
1113.1
148.4
0.521


Zr40Ti25Be27Cu8
579.4
737.5
1080.0
158.1
0.536


Zr40Ti25Be25Cu10
579.4
743.2
1046.9
163.8
0.553


Zr27.5Ti35Be29.5Cu8
590.9
728.6
1107.5
137.7
0.534


Zr32.5Ti30Be31.5Cu6
590.4
739.7
>1123.2
149.3
<0.526


Zr32.5Ti30Be29.5Cu8
587.7
745.1
1092.9
157.4
0.538


Zr32.5Ti30Be27.5Cu10
587.8
747.4
1061.2
159.6
0.554


Zr37.5Ti25Be27.5Cu10
584.0
744.1
1080.2
160.1
0.541


Zr30Ti30Be32Cu8
591.2
736.0
1123.2
144.8
0.526


Zr30Ti30Be30Cu10
596.0
740.4
1046.0
144.4
0.570


Zr35Ti25Be32Cu8
596.5
735.4
1021.2
138.9
0.584


Zr35Ti25Be30Cu10
595.0
746.1
989.2
151.1
0.601


Zr35Ti25Be28Cu12
596.3
744.0
984.6
147.7
0.606


Zr40Ti20Be26.25Cu13.75
589.5
740.8
1114.7
151.3
0.529


Zr35Ti30Be33Co2
584.3
721.0
1097.3
136.7
0.532


Zr35Ti30Be31Co4
588.7
740.4
1075.1
151.7
0.548


Zr35Ti30Be29Co6
597.3
749.4
1110.5
152.1
0.538


Zr35Ti30Be33Fe2
586.0
722.8
1100.8
136.8
0.532


Zr35Ti30Be31Fe4
591.7
737.8
1073.7
146.1
0.551









Although the above discussion has focused on the formulation and properties of the TPF alloy of the current invention, the invention is also directed to novel techniques for forming and shaping such materials. It should be understood as a starting point that the formation of the alloy materials and the shaping of those materials may either be intertwined or separate processes, and in the case where separate processes are used to make the alloy material and then form that material into a final product any suitable process may be used to make the alloy starting material.
For example, in one common process nominal compositions are made into ingots by melting the mixtures in an arc furnace under an inert gas atmosphere. The alloy ingots are then cast into cavities with different shapes within a conductive mold to render the solidified product amorphous. In such an embodiment material parts or articles can be made by thermoplastically processing the amorphous sheets or amorphous starting materials with any suitable thermoplastic processing technique as will be discussed in the following section. It should be understood in reading the following methods that any suitable method of making a feedstock of material may be used, such as, for example, by a drop tower method, etc.
In one embodiment, the method of thermoplastically processing an amorphous alloy may comprise a plastic molding process including the steps of:

    
    
        providing a quantity of a metallic glass in an amorphous state in the ambient temperature; heating said amorphous alloy directly to an intermediate thermoplastic forming temperature range above Tg and below the Tnose;
        stabilizing the temperature of the amorphous alloy within the intermediate thermoplastic forming temperature range;
        shaping the amorphous alloy under a shaping pressure low enough to maintain the amorphous alloy in a Newtonian viscous flow regime and within the intermediate thermoplastic forming temperature for a period of time sufficiently short to avoid crystallization of the amorphous alloy to form a molded part; and
        cooling the molded part to ambient temperature.
    
    


In another embodiment, the method of thermoplastically processing an amorphous alloy may comprise a plastic casting process including the steps of:

    
    
        providing a quantity of an amorphous alloy in a molten state above the melting temperature of the amorphous alloy (Tm);
        cooling said molten amorphous alloy directly to an intermediate thermoplastic forming temperature range above Tg and below the Tnose;
        stabilizing the temperature of the amorphous alloy within the intermediate thermoplastic forming temperature range;
        shaping the amorphous alloy under a shaping pressure low enough to maintain the amorphous alloy in a Newtonian viscous flow regime and within the intermediate thermoplastic forming temperature for a period of time sufficiently short to avoid crystallization of the amorphous alloy to form a molded part; and
        cooling the molded part to ambient temperature.
    
    


In still another embodiment, the method of thermoplastically processing an amorphous alloy comprises an injection molding process. For clarity, the steps of this process are overlaid on a TTT diagram in FIG. 4. As shown, the process includes the steps of:

    
    
        heating/cooling an amorphous feedstock to a temperature between the glass transition temperature, Tg, and the crystallization temperature, Tx (FIG. 4, Step 1);
        forcing the heated alloy through a restrictive nozzle before entrance into a mold (FIG. 4, Step 2); and
        cooling the molded part to an ambient temperature (FIG. 4, Step 3).
    
    


The injection molding process requires several additional components including a reservoir for the amorphous feedstock, a method of heating the amorphous metallic feedstock, a method of applying pressure to the material in the reservoir, a gate or gating system, a mold and optionally a method of heating the mold. One exemplary embodiment of such a system is diagrammed schematically in FIG. 5. As shown, a reservoir (10) of molten alloy is attached via a gate and nozzle (12) to a mold (14). A pressure, in this case via a plunger mechanism (16) is then applied to the alloy in the reservoir to inject it through the gate/nozzle into the mold.
Although any suitable method of heating the amorphous feed stock may be used with the injection molding process of the current invention, some exemplary methods include, but are not limited to an RF power supply and coil, a cartridge heater, and a furnace.
Likewise, suitable methods of applying pressure to the material in the reservoir may include, but are not limited to, a piston, a plunger, and a screw drive.
Although injection molding is generally considered more complicated to perform than the conventional casting/molding processes described above, there are several significant advantages that make it attractive. For example, the most common method of obtaining metallic glass parts is die casting where the molten alloy is injected into a mold and then cooled below the glass transition temperature sufficiently fast to avoid crystallization. However, die casting requires the molten alloy to be rapidly quenched while being molded in order to effectively bypass crystallization. This processing route thus takes advantage of the thermodynamic stability of the alloy at temperatures above the crystallization nose (the point labeled as Tn in FIG. 2), which provides the temperature Tn at which an alloy has the minimum time to crystallization. However, using such a technique can introduce flow defects into the sample such as micro-cavities, due to high inertial forces in relation to the surface tension forces during the injection of the low viscosity molten liquid. High inertial forces in relation to surface tension forces give rise to a Rayleigh-Taylor instability and consequent flow break-up, resulting in void entrapment. Cavities are also found in the center of die cast parts because parts are vitrified through contact with a mold from the outside in, and cavities nucleate in the center due to the built-up of negative pressure. This phenomenon is shown schematically in FIG. 3. Other undesirable defects can also be found in parts fabricated by the die casting method such as high residual stress concentrations, arising due to a strong coupling between high speed flow and rapid cooling. The flow and cooling requirements of die casting also bound the dimensions of die cast parts to no larger than that which can be cooled sufficiently fast to avoid crystallization and no smaller than that which can be quickly filled. Accordingly, parts with complex geometries, thin sections, and high aspect ratios are difficult to obtain with die casting.
As described above, plastic processing techniques where an amorphous feedstock is heated to a temperature between Tg and Tx and formed under pressure also exist. These methods generally take advantage of the kinetic stability of the alloy at temperatures below the crystallization nose (see, e.g., FIG. 5). Plastic processing also takes advantage of lower processing temperatures resulting in relatively lower oxidation rates These methods include the forming of amorphous metal sheets (see, e.g., U.S. Pat. No. 6,027,586, the disclosure of which is incorporated herein by reference), the compaction of amorphous powders (see, e.g., U.S. Pat. No. 5,209,791, the disclosure of which is incorporated herein by reference), the extrusion of amorphous feedstock into a die (see, e.g., K. S. Lee, Y. W. Chang, 2005, the disclosure of which is incorporated herein by reference), and the imprinting of amorphous metal (see, e.g., Y. Saotome, et al., 2002, the disclosure of which is incorporated herein by reference). While most of these routes reduce the defects of the processed amorphous part, each has other limitations. For example, forming amorphous metal sheets limits the thickness of the final sample and the available part geometries, powder compaction methods usually produce parts having micro- or nano-dispersed porosity that often results in inferior mechanical properties compared to homogenously-solidifying parts, free extrusion, or extrusion into a die only allows parts with simple geometries to be fabricated, and imprinting methods enable very small features to be replicated, but are incapable of producing bulk parts.
The present invention utilizes the ability of the TPF metallic glasses of the current invention to flow homogeneously at temperatures between Tg and Tx, to enable pressurized injection of the alloy into a mold to produce a homogenous bulk part with no size restrictions. Another method that utilizes the flow capabilities of metallic glasses between Tg and Tx has been invented by Johnson (See, U.S. Pat. No. 7,017,645, the disclosure of which is incorporated herein by reference). That method involves cooling the molten alloy from above the melting point to a temperature between the crystallization nose and Tg, molding at this intermediate temperature, and cooling to ambient temperature. Although this method has similar advantages to the present invention in terms of achievable part geometries and final porosity, Johnson's method requires bypassing the crystallization nose during processing necessitating complicated setups comprising hermetically sealed nozzles and diffusers. Another disadvantage of Johnson's method is the smaller thermal driving force available to quench at an intermediate temperature before processing, as opposed to the current invention where an amorphous feedstock can be quenched to room temperature and later reheated for processing. As a result, Johnson's method necessitates the use of alloys that exhibit high stability against crystallization at Tn whereas the method according to this invention leaves open the possibility of using a broader range of alloys.
The following examples are provided to demonstrate the improved thermoplastic forming properties of the alloys of the instant invention. Specifically tests were performed to investigate the thermal, rheological, and crystallization (Time-Temperature-Transformation (TTT)-diagrams) properties of the inventive material. In summary these studies show that the alloys of the current invention exhibit high yield strength, excellent fracture toughness, and a relatively high Poisson's ratio. In addition, simple micro-replication experiments carried out in open air using relatively low applied pressures demonstrate superior thermoplastic processability for engineering applications.
EXAMPLES
Example 1
Alloy Formation and Properties
Although any suitable alloy formation process may be used to form the materials of the current invention, in the following examples mixtures of elements of purity ranging from 99.9% to 99.99% were alloyed by induction melting on a water cooled copper boat under a Ti-gettered argon atmosphere. Typically 5 g ingots were prepared. Each ingot was flipped over and re-melted at least three times in order to obtain chemical homogeneity.
A Philips X'Pert Pro X-ray diffractometer and a Netzsch 404C differential scanning calorimeter (DSC) (performed at a constant heating rate 0.33 K/s) were utilized to confirm the amorphous natures and to examine the isothermal behaviors in the SCLR of these alloys.
The viscosity of Zr35Ti30Cu7.5Be27.5 as a function of temperature in the SCLR was studied using a Perkin Elmer TMA7 in the parallel plate geometry as described by Bakke, Busch, and Johnson. (E. Bakke, R. Busch, W. L. Johnson, Applied Physics Letters 1995, 67, 3260, the disclosures of which are incorporated herein by reference.) The measurement was done with a heating rate of 0.667 K/s, a force of 0.02 N, and an initial height of 0.3 mm. The Viscosity and Temperature-Time-Transformation (TTT) diagrams of Zr35Ti30Cu7.5Be27.5 at high temperatures were measured in a high vacuum electrostatic levitator (ESL). (See, S. Mukherjee, et al., Acta Materialia 2004, 52, 3689; and S. Mukherjee, et al., Applied Physics Letters 2004, 84, 5010, the disclosures of which are incorporated herein by reference.) For the viscosity measurements, the resonant oscillation of the molten drop was induced by an alternating current (AC) electric field while holding the sample at a preset temperature. Viscosity was calculated from the decay time constant of free oscillation that followed the excitation pulse.
To determine the top half of the TTT curve, an electrostatically levitated molten (laser melting) droplet ( ̃3 mm diameter) sample was cooled radioactively to a predetermined temperature, and then held isothermally until crystallization. The temperature fluctuations were within ±2 K during the isothermal treatment. For temperatures below the nose of the TTT curve, data was obtained by heating the alloy at 40 K/min in a graphite crucible to the desired temperature and holding the sample isothermally until crystallization.
Using the above techniques studies were performed on the physical properties of alloys in the two “preferred” composition regions of the current invention. As previously discussed, these “preferred” regions include alloys that have compositions in accordance with the following formula: ZraTibCucBed (60%<a+b<80%), where in the first region a≈b and d>15%; and where in the second region a≈5b and d>20%
The differential scanning calorimetry (DSC) curves of three representative alloys of the current invention are presented in FIG. 6. The DSC scans (at a constant heating rate of 0.33 K/s) of three typical metallic glasses with good glass forming ability and high thermal stability against crystallization are presented. The 5-g samples were made in a Ti-gettered silver boat and were generally found to freeze without any crystallization during preparation resulting in a glassy ingot, which suggests that the critical casting thickness of these alloys is at least 1.5 cm. The downward arrows refer to the glass transition temperatures. As shown, the alloys all exhibit a very large SCLR with a single sharp crystallization peak at which the alloy undergoes massive crystallization to a multiphase crystalline product.
The amorphous nature of all the samples studied in this work has been confirmed by X-ray diffraction. A summary of thermal properties of these alloys are listed in Table 2 below, and compared with several earlier reported amorphous alloys.







TABLE 2







Thermal property comparison of various BMG forming alloys.














Tg
Tx
Tl
ΔT




Materials
(K)
(K)
(K)
(K)
Tg/Tl
TTPF
















Zr35Ti30Cu7.5Be27.5
575
740
1071
165
0.537
600-710


Zr41.2Ti13.8Ni10Cu12.5Be22.5
623
712
993
89
0.627
640-690


Zr46.75Ti8.25Ni10Cu7.5Be27.5
625
738
1185
113
0.527
650-710


Pd43Ni10Cu27P20
575
665
866
90
0.664
600-640


Pt60Ni15P25
488
550
804
60
0.596
510-530


Ce68Cu20Al10Nb2
341
422
643
81
0.530
360-400


Au49Ag5.5Pd2.3Cu26.9Si16.3
401
459
644
58
0.623
420-440


Pt57.5Cu14.7Ni5.3P22.5
508
606
795
98
0.639
530-580





References: A. Peker, W. L. Johnson, Applied Physics Letters 1993, 63, 2342; B. Zhang, et al., Physical Review Letters 2005, 94, 205502; T. A. Waniuk, et al., Applied Physics Letters 2001, 78, 1213; H. Kato, et al., Scripta Materialia 2006, 54, 2023; K. Shibata, et al., Progress of Theoretical Physics Supplement 1997, 126, 75; and J. Schroers, et al., Applied Physics Letters 2005, 87, 061912, the disclosures of each of which are incorporated herein by reference.)






The variations of SCLR, ΔT, (ΔT=Tx-Tg, in which Tx is the onset temperature of the first crystallization event) and reduced glass transition temperature Trg (Trg=Tg/Tl, where Tl is the liquidus temperature) are calculated. In the alloys of the current invention, Zr35Ti30Cu7.5Be27.5 exhibits the lowest Tg (575 K and about 50 K lower than that of Vitreloy 1 or Vitreloy 4) and the largest ΔT. It was further found that the ΔT of the same glass can be maintained at  ̃165 K by addition of 0.5% Sn, providing the largest SCLR reported for any known bulk metallic glass.
In FIG. 7, the temperature dependence of equilibrium Newtonian viscosity of on exemplary alloy of the current invention (Zr35Ti30Cu7.5Be27.5) and several other metallic glass forming liquids are presented. In the figure, the following symbols are used for the different materials: Zr41.2Ti13.8Ni10Cu12.5Be22.5 (Vit1) (Δ); Zr46.25Ti8.25Cu7.5Ni10Be27.5 (Vit4)  Zr35Ti30Cu7.5Be27.5 (□); Pd43Ni10Cu27P20 (x); and Pt60Ni15P25 (⋄). The solid curve represents a Vogel-Futcher-Tammann (VFT) fit to the viscosity data of Zr35Ti30Cu7.5-Be27.5 in accordance with the following equation:




  
    
      
        
          η
          =
          
            
              η
              
                0
                ⁢
                
                  
                
              
            
            ⁢
            
              exp
              ⁡
              
                (
                
                  
                    
                      
                    
                    ⁢
                    
                      
                        D
                        *
                      
                      ·
                      
                        T
                        
                          0
                          ⁢
                          
                            
                          
                        
                      
                    
                  
                  
                    T
                    -
                    
                      T
                      0
                    
                  
                
                )
              
            
          
        
        ,
      
    
    
      
        [
        
          EQ
          .
          
            
          
          ⁢
          1
        
        ]
      
    
  




where η0, D*, and T0 are fitting constants. T0 is the VFT temperature and η0≈10−5 Pa s. In the best fit, T0=422.6 K and D*=12.4 are found. The alloy in accordance with the current invention shows a viscosity in the thermoplastic zone (570 ̃720 K) that is at least two orders of magnitude lower than that of Vitreloy 1 or Vitreloy 4 at the same temperature and is comparable to that of Pd-based metallic glass, but with a larger ΔT. For example, the equilibrium viscosity at 410° C. for Zr35Ti30Cu7.5Be27.5 is measured to be only 6*104 Pa·s, similar to that of viscous polymer melts. (See, F. W. Billmeyer, Textbook of Polymer Science, 1984, 305, the disclosure of which is incorporated herein by reference.) As is known from the processing of thermoplastics, the formability is inversely proportional to viscosity. Accordingly, the low viscosity in the SCLR of the TPF alloy of the current invention will result in a low Newtonian flow stress and high formability. Therefore, the present alloys are much more preferable for thermoplastic processing than the traditional Vitreloy 1 series.

In FIG. 8, we present the measured TTT curve for Zr35Ti30Cu7.5Be27.5 and other Vitreloy series alloys. (T. Waniuk, et al., Physical Review B 2003, 67, 184203, the disclosure of which is incorporated by reference.) In the figure, the following symbols are used for the different materials: Zr41.2Ti13.8Ni10Cu12.5Be22.5 (Vit1) (x); Zr46.25Ti8.25Cu7.5Ni10Be27.5 (Vit4) (*); Zr44Ti11Cu10Ni10-Be25 (Vit1b) (+)) and the selected Zr35Ti30Cu7.5Be27.5 alloy (□ and Δ). The data are measured by electrostatic levitation (□) and by processing in graphite crucibles (other than □) after heating from the amorphous state. The processing window can be identified from this TTT diagram. Specifically, the TTT curve indicates a nose shape, with the minimum crystallization time of  ̃3-10 s occurring somewhere between 700 K and 950 K. At 680 K, where the equilibrium viscosity is on the order of 104 Pa s, a 600-s thermoplastic processing window is indicated. Based on the curves it can be estimated that the exemplary TPF alloy should have a processing time of about 2 minutes at around 700 K without risking crystallization.
To demonstrate the good thermoplastic processability of the exemplary TPF alloy (Zr35Ti30Cu7.5Be27.5) glassy alloy, thermoplastic imprinting experiments were performed as shown in FIGS. 9a to 9d. The thermoplastic processing was done on a Tetrahedron hot press machine in the air at a pressure of 25 MPa with a processing time of 45 s, followed by a water-quenching step. FIG. 9 shows the microformed impression of a United States dime coin (FIG. 9b) made on the surface of metallic glass wafers at  ̃370° C. (FIG. 9a) indicating the excellent imprintability and viscous deformability of the material. In addition, minimal oxidation was observed after the processing which is consistent with the strong oxidation resistance of Be-bearing amorphous alloys. Finally, the final parts remain fully amorphous as verified by X-ray diffraction. It is further found from the Rockwell hardness tests that no damage to the mechanical properties of the alloy was caused by the thermoplastic processing.
Before the TPF was carried out, diamond-shape micro-indentation patterns ( ̃100 μm) were deliberately imprinted into the wafer in the top flame of the dime using a Vickers hardness tester (FIG. 9c). FIG. 9d presents the successfully replicated diamond pattern in the final part. Even the scratches (on the level of several μm) on the original dime are clearly reproduced. The results indicate a substantial advance in thermoplastic processing of amorphous metals.
Accordingly, the metallic glass forming alloys of the current invention have a combination of properties ideally suited for TPF processes, such as extraordinarily low viscosity in the thermoplastic zone, exceptional thermal stability, very low Tg, and excellent GFA. These alloys have also demonstrated strong thermoplastic processability and excellent mechanical properties providing for the possibility of broadening the engineering applications of amorphous metals generally.
Example 2
Injection Molding Application
As discussed above, the current invention is also directed to novel methods of forming the TPF alloys of the current invention. In FIG. 10 photographs are provided of parts made in accordance with the novel injection molding process disclosed herein next to a polymer part created from the same mold. (From top to bottom: Top Metallic glass Zr35Ti30Cu7.5Be27.5 injected at 400 C with 10000 PSI, 2nd same glass injected at 380 C with 45000 PSI, 3rd same glass injected at 420 C with 45000 PSI, and 4th Polymer part injected at 220 C with 5000 PSI, all parts are as cast.) Slight polishing after molding with 320 grit paper removes any oxide layer.
Due to the viscous nature of metallic glasses in the region between Tg and Tx, the sprue and nozzle commonly used for plastic injection molding were replaced by a thin washer that acted as a nozzle. The TPF alloy Zr35Ti30CU7.5Be27.5, in accordance with the current invention was used as the amorphous feedstock to demonstrate the injection molding process because it provides the largest supercooled liquid region (SCLR) (Tx−Tg=165 C) of any alloy to date and also the lowest attainable viscosity in the SCLR ( ̃104 Pa-s) of any known metallic glass. The flashing is 0.1 mm thick and 2.5 mm wide, and was formed mainly due to the lack of adequate clamping force during the process. In this exemplary embodiment both sides of the mold were not filled due to insufficient space in the reservoir for enough material. These final parts demonstrate that a true injection molding process can be used with the TPF alloy materials of the current invention opening up new applications for these alloys in industry.
FIG. 11 shows three point beam bending tests of 2 mm×2 mm×20 mm injection molded specimens and die cast specimens of Zr35Ti30Cu7.5Be27.5. The average value of the modulus of rupture is nearly equal for both processing methods, but the standard deviation of the modulus of rupture for the cast samples (2.879+/−0.240 GPa) is 3.7 times larger than that of the injection molded specimens 12.923+/−0.065 GPa). FIG. 12 provides a fit of the modulus of rupture data to obtain the Weibull modulus for the injection molded specimens and die cast specimens of Zr35Ti30Cu7.5Be27.5. Weibull modulus is basically a measure of the reproducibility of parts. Weibull statistics assume that failure initiates from defects in the sample. Accordingly, samples with low Weibull modulus have high numbers of defects per unit volume. In the current test the injection molded parts made have Weibull modulus value of mIM=41.9, while the die cast parts have a Weibull modulus of mDC=9.74. As a comparison, high quality engineering ceramics have Weibull modulus values of 1-10, while most metals have Weibull modulus numbers greater than 100.
Both the modulus of rupture test and the Weibull modulus fit are evidence of the improved mechanical properties and reproducibility of fabricated part strengths due to the nearly defect free structures found in parts produced by the injection molding technique of the current invention.
SUMMARY
In summary, a new class of high strength, thermoplastically processable amorphous alloys having low density, viscosities in the thermoplastic zone at least two orders of magnitude lower than that of the commercialized Zr-based alloys and similar to the viscosity of Pd-based metallic glass and polymer glasses, unusually high thermal stability, low Tg, and excellent glass forming ability (critical casting thickness  ̃15 mm) have been discovered. In addition, an injection molding technique has been developed to allow processors to take full advantage of the unique properties of these materials The technological potential of this class of glassy alloys and the injection molding technique is very promising in a wide-variety of applications including, for example, aerospace and astrospace components (Ribs, spars, airframes, space structures), defense (Armor plating, weapons), sporting goods (tennis rackets, baseball bats, golf clubs), structural components (frames, casings, hinges), automotive components, foam structures, nano- and microtechnology, medical and optical applications, data storage, and microelectromechanical systems.
Finally, it should be understood that while preferred embodiments of the foregoing invention have been set forth for purposes of illustration, the foregoing description should not be deemed a limitation of the invention herein. Accordingly, various modifications, adaptations and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present invention.

## Claims

1. A thermoplastically processable bulk solidifying amorphous alloy having a composition in accordance with the equation:


(ZrxTi(1-x))a1ETMa2Cub1LTMb2Bec,

where (ETM) comprises the group of Early Transition Metals, (LTM) comprises the group of Late Transition Metals;
where x is an atomic fraction and a1, a2, b1, b2, and c are atomic percentages, and where (a1+a2) falls within the range of 60 to 80%, x is in the range of 0.05 to 0.95, (b1+b2) is in the range of 2 to 17.5%, c is at least 15%, and Ni comprises no greater than 5% of the overall composition; and
where the alloy has a supercooled liquid region (ΔT) defined as the temperature difference between the glass transition temperature and crystallization temperature of the alloy of at least 135 K and a viscosity within this supercooled liquid region that falls below a value of less than about 105 Pa-s when measured at a heating rate of 20 K/min.

2. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a composition in accordance with the following equation:


ZraTibCucBed; and

wherein a, b, c, and d are atomic percentages, a+b is within the range of 60 to 80%, and d is greater than or equal to 15%.

3. The thermoplastically processable bulk solidifying amorphous alloy of claim 2, wherein a is approximately equal to five times b and d is greater than or equal to 20%.

4. The thermoplastically processable bulk solidifying amorphous alloy of claim 2, wherein a is approximately equal to b.

5. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the atomic percent of Zr and Ti is in the range of from about 60 to 75%.

6. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, further comprising up to 5% of at least one additional material.

7. The thermoplastically processable bulk solidifying amorphous alloy of claim 6, wherein the additional material is selected from the group consisting of tin, boron, silicon, aluminum, indium, germanium, gallium, lead, bismuth, arsenic and phosphorous.

8. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, further comprising up to 15% of at least one additional early transition metal.

9. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the early transition metal is selected from the group consisting of chromium, hafnium, vanadium, niobium, yttrium, neodymium, gadolinium and other rare earth elements, molybdenum, tantalum, and tungsten.

10. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, further comprising up to 15% of at least one additional late transition metal.

11. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the early transition metal is selected from the group consisting of manganese, iron, cobalt, ruthenium, rhodium, palladium, silver, gold, and platinum.

12. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has an amorphous phase that comprises greater than 25% of the alloy by volume.

13. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has an amorphous phase that comprises greater than 90% of the alloy by volume.

14. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a density of around 5.5 g/cm3.

15. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a supercooled liquid region of greater 140 K when measured at a heating rate of 20 K/min.

16. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein at a heating rate of 20 K/min the alloy attains a viscosity in the supercooled liquid region of lower than 104 Pa-s.

17. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a critical cooling rate of less than 106 K/s.

18. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a critical cooling rate of less than 103 K/s.

19. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the composition has a ΔT of at least 160 K and is selected from the group consisting of Zr35Ti30Cu7.5Be27.5, Zr37.5Ti25Cu10Be27.5, and Zr40Ti25Cu10Be25.

20. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a critical casting thickness of greater than 1 mm.

21. The thermoplastically processable bulk solidifying amorphous alloy of claim 1, wherein the alloy has a critical casting thickness of greater than 15 mm.

22. A thermoplastically processable bulk solidifying amorphous alloy having a composition in accordance with the equation:


(ZrxTi(1-x))a1ETMa2Cub1LTMb2Bec,

where (ETM) comprises the group of Early Transition Metals, (LTM) comprises the group of Late Transition Metals;
where x is an atomic fraction and a1, a2, b1, b2, and c are atomic percentages, and where (a1+a2) falls within the range of 60 to 75%, x is in the range of 0.50 to 0.85, (b1+b2) is in the range of 2 to 17.5%, c is in the range of 17.5 to 33%, and Ni comprises no greater than 5% of the overall composition; and
where the alloy has a supercooled liquid region (ΔT) defined as the temperature difference between the glass transition temperature and crystallization temperature of the alloy of at least 135 K and at a heating rate of 20 K/min has a viscosity within this supercooled liquid region that falls below a value of less than about 105 Pa-s.

23. The thermoplastically processable bulk solidifying amorphous alloy of claim 22, wherein the alloy has a composition in accordance with the following equation:


ZraTibCucBed; and

wherein a, b, c, and d are atomic percentages, a+b is within the range of 60 to 65%, c is in the range of 5 to 17.5%, and d is in the range of 17.5 to 32%.

24. The thermoplastically processable bulk solidifying amorphous alloy of claim 23, wherein a is approximately equal to five times b and d has a lower limit of 20%.

25. The thermoplastically processable bulk solidifying amorphous alloy of claim 22, further comprising up to 5% of at least one additional material.

26. The thermoplastically processable bulk solidifying amorphous alloy of claim 25, wherein the additional material is selected from the group consisting of tin, boron, silicon, aluminum, indium, germanium, gallium, lead, bismuth, arsenic and phosphorous.

27. The thermoplastically processable bulk solidifying amorphous alloy of claim 22, wherein the early transition metal is selected from the group consisting of chromium, hafnium, vanadium, niobium, yttrium, neodymium, gadolinium and other rare earth elements, molybdenum, tantalum, and tungsten.

28. The thermoplastically processable bulk solidifying amorphous alloy of claim 22, wherein the late transition metal is selected from the group consisting of manganese, iron, cobalt, ruthenium, rhodium, palladium, silver, gold, and platinum.

29. The thermoplastically processable bulk solidifying amorphous alloy of claim 22, wherein the composition has a ΔT of at least 160 K and is selected from the group consisting of Zr37.5Ti25Cu10Be27.5, Zr40Ti25Cu10Be25, and Zr35Ti30 Cu7.5Be27.5.