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REVIEW

Processing of Bulk Metallic Glass


By Jan Schroers*

Bulk metallic glass (BMG) formers are multicomponent alloys that vitrify with remarkable ease during solidication. Technological interest in these materials has been generated by their unique properties, which often surpass those of conventional structural materials. The metastable nature of BMGs, however, has imposed a barrier to broad commercial adoption, particularly where the processing requirements of these alloys conict with conventional metal processing methods. Research on the crystallization of BMG formers has uncovered novel thermoplastic forming (TPF)-based processing opportunities. Unique among metal processing methods, TPF utilizes the dramatic softening exhibited by a BMG as it approaches its glass-transition temperature and decouples the rapid cooling required to form a glass from the forming step. This article reviews crystallization processes in BMG former and summarizes and compares TPF-based processing methods. Finally, an assessment of scientic and technological advancements required for broader commercial utilization of BMGs will be made.

1. Introduction
The discovery of metallic glasses in 1960[1] triggered a ood of research on glass formation (see, e.g., ref. [2]). The knowledge obtained from these studies of glass-forming systems was used to develop metallic alloys with increasingly higher glass-forming ability, culminating in the synthesis of bulk metallic glasses (BMGs).[3] BMG formers are arbitrarily dened as alloys that can be cast into a fully amorphous solid whose smallest dimensions is at least 1 mm. Though scientically interesting, the rst BMGs were formed from relatively exotic constituents and, thus, were not useful for the vast majority of practical engineering applications. This changed, however, with the discovery by Inoue and co-workers at the Tohoku University of technologically more relevant BMG formers based on magnesium,[4] lanthanum,[5] and zirconium,[6] as well as the discovery led by Johnson and co-workers at Caltech of additional Zr-based BMG formers.[7,8] The sluggish crystallization kinetics exhibited by BMG formers enabled the characterization of various thermophysical properties of the undercooled liquid such as specic heat,[9,10] diffusion,[1114] viscosity,[1519] atomic motion,[20,21] emissivity,[22] and crystallization,[2328] often over the entire temperature range from the
[*] Prof. J. Schroers Yale University Mechanical Engineering New Haven, CT 06511 (USA) E-mail: jan.schroers@yale.edu

DOI: 10.1002/adma.200902776

liquidus to the glass-transition temperature. These research results, together with advancements in the understanding of glass formation,[2933] have been used to develop a wide range of BMG-forming compositions based on, for example, Ti,[34,35] Cu,[36,37] Fe,[3840] Ni,[41,42] Pd,[4345] Zr,[68,46,47] Au,[48,49] Ce,[50] Pt,[51] Ca,[52] and Mg[4,53,54] often with improved processability relative to earlier alloys. The results of crystallization studies also led to the development of unique processing methods, which take advantage of the sluggish kinetics of BMG. Although some (bulk) metallic-glass formers with soft magnetic properties have been used quite successfully and widespread in high-frequency transformers,[55,56] structural applications have long been proposed as their main eld of application.[5760] The random atomic structure and concomitant lack of dislocations and associated slip planes in BMGs result in very high strength and elasticity; compressive yield strengths of approximately 2 GPa and elasticities of 2% are typical for Zr-based BMG formers,[57] and yield strengths of up to 5 GPa have been reported for some exotic BMG formers.[61] Upon yielding, however, BMGs suffer from a strong tendency toward shear localization, which results in macroscopically brittle failure at ambient temperatures (see, e.g., ref. [58]). Shear localization leading to shear band formation is generally recognized to be a consequence of the absence of a strain-hardening mechanism, whereas strain softening due to the creation of free volume during the shearing precedes localization of shear. With the exception of some recently developed BMG formers that exhibit a reduced tendency to shear localization and thereby global plasticity,[6268] for the majority of BMG formers shear band formation results in catastrophic failure along a dominant shear band and prevents any noticeable macroscopic plasticity. However, when BMG samples with small dimensions are characterized, signicant global plasticity is observed.[6971] For example, when at least one dimension approaches the length scale of the processing zone, the plastic zone in front of a crack tip, which for some BMGs can be in the order of millimeters,[62] samples exhibit signicant plasticity in bending.[72,73] For most applications, bending is the dominant loading condition. The critical crack length in BMGs varies from approximately 10 mm for brittle BMG formers[7476] to over 1 mm for the toughest BMGs.[62] Therefore, to realize the full range of attractive properties, BMG formers should be used in geometries where at least one dimension approaches the length scale of the processing zone.

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Processing of BMG formers requires special attention. The main challenge is to avoid crystallization during processing and solidication. Hence, an understanding of the crystallization process in BMG forming alloys is necessary to develop fabrication processes. The nature of the crystallization mechanism, the effect of heterogeneities on the crystallization kinetics, as well as the reproducibility of the crystallization process all have to be considered (for more detailed discussions of these see Ref. [7779]). The difference in the temperature dependence between the viscosity and driving force for crystallization results in a nose-shaped timetemperature-transformation (TTT) curve (see, e.g., ref. [80]). As a consequence of their crystallization behavior, BMG formers can be processed via two principally different paths.[81] One is direct casting, where the alloy must be cooled sufciently fast to avoid crystallization while, at the same time, lling a mold cavity. As ideal molding conditions require slow lling, which is problematic when fast cooling is necessary, only a limited range of geometries can be fabricated through direct casting of BMGs using a careful balance of processing parameters.[82,83] Alternatively, BMGs can be reheated and formed in the supercooled liquid region (SCLR), the temperature region where the glass relaxes into a metastable liquid before it eventually crystallizes. The considerable softening of a BMG forming alloy in its SCLR can be used for thermoplastic forming (TPF). To date, a number of processing methods based on TPF have been developed and these will be reviewed in this article. Due to recent advances in BMG alloy and TPF-based process development, some BMG formers can be considered highstrength alloys that can be processed like plastics.[82] This Review will rst discuss the unique crystallization behavior of BMG formers and how this dictates required processing conditions and methods. These TPF-based methods will then be discussed and compared in terms of the geometrical range of articles they can produce, their dimensional accuracy, reliability, yield, economics, environmental impact, scalability, and their level of maturity as a commercially viable fabrication method.

Jan Schroers is an Associate Professor in the Department of Mechanical Engineering at Yale University. He received his Ph.D. in Physics from the RWTH Aachen. After joining Bill Johnsons group at Caltech for four years as a post-doc, he spent three years with Liquidmetal Technologies as a Director of Research, where he developed novel processing methods based on the thermoplastic formability of bulk metallic glasses. His research focuses on amorphous metals, foams and composites, combinatorial material science, MEMS and nanofabrication, biomedical implants and devices, and articial microstructures as models to investigate microstructureproperty relations.

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2. Crystallization
Glass formation requires that crystallization is avoided during solidication and processing. Cooling a melt below its liquidus temperature, Tl, results in an increase in the driving force for crystallization, measured by the Gibbs free energy difference between the undercooled melt and competing crystalline phases.[8486] This increasing desire for crystallization with decreasing temperature is accompanied by a decreasing ability to crystallize, which is controlled by the temperature-dependent viscosity (Fig. 1).[87] Generally, both a reduced desire and a reduced ability to crystallize result in better glass forming ability.[84] Since the viscosity exhibits a stronger temperature dependence compared to the Gibbs free energy difference, the crystallization kinetics as a function of temperature go through a maximum (see, e.g., ref. [77]). As a result, this behavior manifests as a nose shape in the TTT diagram.[23,2527,8894] A nose-shaped curve can be expected for all BMG-forming systems (see, e.g., ref. [80]). A TTT diagram depicts the time until crystallization sets in for a given temperature (i.e., for isothermal conditions). Strictly speaking,

under (constant)-cooling conditions, which more often apply when considering real casting processes, a constant-cooling diagram should be used to predict crystallization behavior.[95] However, the strong temperature dependence of the crystallization time results in a narrow TTT curve; as a consequence, both the constant-cooling curve and the TTT curve generally appear similar in shape.[8991] Figure 2A depicts some representative TTT diagrams in schematic form, illustrating how increasing ability and desire to crystallize affect the position of the TTT diagram on the time axis. For example, the nose of the TTT diagram for a pure metal, with the highest ability and desire to crystallize, lies at $108 s. For a marginal glass former the nose shifts to longer times, $104 s, ultimately reaching as low as $10 s for a BMG. The synergistic development of BMGs with sluggish crystallization kinetics and processing methods that reduce heterogeneous inuences on crystallization has enabled the characterization of BMG forming liquids on an experimentally practical time scale. As an example, Figure 2B depicts the experimentally determined TTT diagram of Zr58.5Nb2.8Ni12.8Cu15.6Al10.3.[26] Table 1 summarizes the BMG formers for which TTT diagrams covering the entire temperature region between the BMGs liquidus temperature and its glass transition temperature have been determined. The TTT diagrams summarized in Table 1 were determined from samples that were cooled from a temperature above Tl down to the isothermal temperature. TTT diagrams have also been obtained by heating the BMG former from ambient temperature up to the isothermal temperature.[18,89,9799] At low temperatures (see Fig. 2B), the crystallization kinetics revealed in the TTT diagrams determined by both heating and cooling coincide. However, with increasing temperature, the time to crystallization, tonset, increasingly differs between the two TTT diagrams. This difference between the two TTTdiagrams measured upon cooling and heating can be explained by the fact that the maximum of the nucleation rate is always at a lower temperature than the maximum of the growth rate (Fig. 2C).[97] During heating, all the nuclei that form at the maximum of the nucleation rate are exposed to the maximum growth rate during further heating. In contrast, during cooling the sample passes through the

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Figure 1. A) Difference in Gibbs free energy, DG, between the liquid and the crystalline state for (bulk) metallic-glass-forming liquids with varying critical cooling rates. B) Angell plot comparing the viscosities of different types of (bulk) metallic-glass-forming liquids, which are depicted together with non-metallic liquids. Reproduced with permission from [84]. Copyright 2007, Materials Research Society.

temperature region where the growth rate is maximized with few or no nuclei, while the nuclei that eventually form at the maximum nucleation rate experience a dramatically lower growth rate. As a consequence, for cooling and heating of identical magnitude a larger volume fraction of crystals forms during heating than cooling.[80,100] Therefore, in order to avoid a detectable crystallization during heating, heating rates that are about two orders of magnitude higher than the cooling rates are required to avoid crystallization.[97] For isothermal crystallization, faster crystallization kinetics are predicted by this model[90,91,97,89,101] when the isothermal temperature is reached through heating from below the glass temperature, Tg. Furthermore, the model predicts that this difference in crystallization behavior between heating- and cooling-derived TTT diagrams increases with increasing temperature,[90,101] as observed experimentally (Fig. 2B). This asymmetry in the TTT

diagrams determined by cooling and heating as well as the associated differences in the critical cooling and heating rate, which we concluded to be present in all metallic systems,[97] have signicant ramications for the processing of BMGs. This is due to the limited temperature range that can be accessed during heating of the BMG former on an experimentally practical time scale. Even though the general shape of the TTT curve tends to be qualitatively similar for most BMG formers, its position on the time axis, which reects the absolute value of the crystallization kinetic varies signicantly. As mentioned previously, the dominant contributions controlling crystallization kinetics are the temperature-dependent viscosity and the driving force for crystallization (see Fig. 1), although other effects such as the compositional change required during non-polymorphic crystallization can also play a crucial role.[102] The temperature dependence of the viscosity is reected in a fragility of the liquid.[103] Fragility varies widely among BMG formers[87,104] and was identied to be the dominant contribution controlling the glass-forming ability.[105] One ubiquitous feature of BMG formers is a tendency toward highly dense packing in the liquid state.[84,106109] A consequence of this dense packing is a high viscosity, particularly in the SCLR.[15,17,87,104,105,110129] This high viscosity contributes to sluggish crystallization kinetics.[105,122,130] The importance of chemical uctuations preceding the nucleation process is often overlooked. BMG formers are multicomponent alloys with an eutectic or close to eutectic composition.[57,131,132] Therefore, the crystallization process is typically non-polymorphic. Consequently, new phases (crystalline) have a different composition than the phase (liquid) they were formed in. This requires chemical uctuation through long-range diffusion to establish regions of the required composition, a phenomenon that was quantied by Desre and coworkers for a system having a positive heat of mixing and zero solubility.[102] Such processes can signicantly retard the crystallization process and might be crucial for bulk-glass formation.[30,32,102,108,133] Interestingly, the interfacial energy, s, has not been identied as a signicant inuence on glass formation although s has a signicant impact on the activation energy, DG* for nucleation (in s2 its simplest form DG / DG3 ). In less complex alloys, however, s is often the phase-selecting contribution when nucleation controls crystallization.[134143] Extensive research has been focused on a mechanistic understanding of crystallization in BMG formers (see, e.g., ref. [77]). The majority of crystallization studies have been carried out in the SCLR temperature region.[24,78,89,91,98,101,144161] Several mechanisms have been proposed to describe the nucleation process of BMG formers in their SCLR, including quenched-in nuclei,[93,162164] nuclei formation through a steady state nucleation rate,[165167] and a transient nucleation process.[168174] The very ne grain size observed in devitried glasses suggests high nucleation densities, in some cases up to 1023 m3.[24,89,97,98,155,175] Generally, a high nucleation rate is associated with rapid crystallization kinetics and, hence, poor glass forming ability, in contradiction to the bulk-glass formation observed in BMG former. To explain this apparent contradiction various mechanisms have been considered. Among them is chemical decomposition (also denoted phase separation), where

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Figure 2. A) Schematic TTT diagram for a pure metal, a marginal glass former, and a BMG former. B) TTT diagram for Zr58.5Nb2.8Ni12.8Cu15.6Al10.3 measured on samples that were cooled from above Tl (blue circles) and heated from below Tg (red squares) prior to the isothermal measurement. Reproduced with permission from [26]. Copyright 2001, American Institute of Physics. C) Temperature dependence of the nucleation (Iss) and growth rate (u). The different positions of the maxima result in the asymmetry of the TTT diagrams measured on samples that are heated from below Tg or cooled from above Tl to the isothermal measurement [97,90]. Reproduced with permission from [97]. Copyright 1999, American Institute of Physics. Table 1. BMG alloys for which a complete TTT diagram has been experimentally determined. Fluxing can signicantly inuence the crystallization kinetics.
Alloy Zr41Ti14Cu12Ni10Be23 Pd40Ni10Cu30P20 Pd43Ni10Cu27P20 Pd43Ni10Cu27P20 Zr58.5Nb2.8Ni12.8Cu15.6Al10.3 [a] Rf radio frequency tnose [s] 50 50 200 130 20 Method Electrostatic levitation Rf-heated graphite container[a] Rf-heated graphite container Rf-heated graphite container Electrostatic levitation Flux No B2O3 B2O3 No No Reference [23,24] [96] [25] [25] [26]

the amorphous phase separates into two (or more) amorphous phases with different chemical composition. Phase separation during devitrication was rst observed during the early days of metallic-glass research[176178] and was explained using Cahns theory of spinodal decomposition.[179] More recently,

decomposition has also been extensively studied in Zr-based BMGs,[[180184] where it has been tightly related to nanocrystallization. However, a complete mechanistic understanding of the involvement of decomposition in the crystallization of BMG formers is still lacking. Decomposition may precede

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crystallization and create a composition, which is more favorable for crystallization,[180,183] but to date only limited evidence has been given to conrm this proposed scenario. In fact, all the experimental results that have been presented so far, fail to provide evidence for a chemically decomposed amorphous phase. Instead, indirect conclusions have been drawn from the observed nanocrystalline microstructure. In some cases decomposition in Zr-based BMG formers was questionable altogether.[185] Furthermore, contradictive conclusions were drawn about decomposition in Pd-based BMG formers because some research results hint at decomposition to be involved in the crystallization,[186] while others did not observe any indication for a decomposition process.[187] For Al-based metallic-glass formers on the other hand, direct evidence for decomposition was provided through transition electron microscopy (TEM) imaging.[188] Indeed, it is surprising to expect phase separation in BMG formers. This is, because one ubiquitous attribute of these alloys is the large negative heat of mixing,[131] promoting the mixing of the constituents and not separating them. However, this argument against decomposition holds only for binary alloys. For multicomponent alloys an overall driving force for decomposition may still exist, even when all components possess a negative heat of mixing among each other. If, for example, two constituents of an alloy have a larger negative heat of mixing among each other than they have with another constituent, they will surround themselves with each other. Thereby, they reject the other species, hence, promoting separation of the species.[189] Alternative mechanisms to decomposition have also been proposed and may explain the high nuclei density.[190] For example, when considering a diffuse solid/liquid interface, it has been concluded that the activation energy for nucleation vanishes at a nite temperature.[190] This model, resulting in a high nucleation rate, describes the experimentally observed high crystal density in Zr-based BMGs much better than other models.[181] The ordered arrangement of crystals upon devitrication has often been considered indirect evidence of a chemical decomposition process involved in the crystallization of BMG forming alloys. Kelton, however, proposed a different mechanism.[151] He argues that the non-polymorphic nature of the crystallization process in BMG forming systems depletes the vicinity around the nucleus from the solute. This depletion decreases the nucleation probability in that region, resulting in an ordered spatial arrangement of crystals, similar to what has been observed experimentally.[191] Bulk-glass formation has been found to be intimately related to quasicrystallization. In various BMG forming systems, including in ZrCuNiAl,[192] ZrCuNiAg,[193] ZrTiCuNiBe,[120,194,195] ZrPd,[196,197] and CuZrTiPd,[198] quasicrystal formation was observed during devitrication. Quasicrystal formation during cooling, however, is a much less common phenomena.[199] The intimate relationship between quasicrystal formation and bulk-glass formation has been explained by the similarities in structure.[106,107,143,192,200205] Similar structure units as the icosahedron, which is present in most quasicrystals such as in tetrahedrons, polyhedrons, and icosahedrons, were observed in BMG forming liquids. An increase of their fraction with

decreasing temperature, approaching the glass transition, was also noted.[204207] It remains to be seen whether the underlying crystallization mechanisms leading to nanocrystallization are ubiquitous among BMG former and to what extend they are controlled by the specics of the alloy. In situ characterization methods might be able to provide some answers. All the above-mentioned crystallization studies were carried out at low temperatures, below the nose of the TTT diagram. In this temperature region the crystallization process is growth controlled.[27] At high temperatures above the nose of the TTT diagram on the other hand, the crystallization mechanism is controlled by nucleation.[27,208] The nature of the crystallization process was revealed through statistical methods, where the scatter in tonset was characterized.[208] Alternatively, the nature of the crystallization mechanism has also been revealed through simultaneously processing of a large number of samples.[27] The corresponding thermogram of the isothermal crystallization experiment of a sample charge consisting of approximately 300 particles is shown in Figure 3. At high temperatures, above the nose of the TTT diagram, the crystallization events of the 300 particles are spread out over one day! However, when processed at low temperatures, below the nose of the TTT diagram, all 300 particles crystallize simultaneously following an internal clock and are undistinguishable form the crystallization of a bulk sample. At high temperatures the large scatter tonset reveals the statistical nature of the crystallization process. The time it takes

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Figure 3. Isothermal DSC thermogram measured on a Pd43Ni10Cu27P20 sample charge comprised of $300 particles. At temperatures above the crystallization nose (shown for 733 K), crystallization of the particles is spread out over one day! This is indicated by the spikes, which correspond to the crystallization of individual particles. Below the nose of the TTT diagram (643 K) all particles crystallize simultaneous, evidenced by the smooth signal, following an internal clock. Reproduced with permission from [27]. Copyright 2001, Elsevier.

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from onset to completion of the crystallization event, tcrystal, is signicantly smaller than tonset. This nding suggests that once a nuclei is formed at tonset, subsequent growth takes only a minor fraction of the overall crystallization time. This is additional evidence for a nucleation-controlled crystallization process, since the vast majority of time is consumed initiating crystallization through a nucleation process. At low temperatures all 300 particles crystallize simultaneously with tonset tcrystal, indicating a well-determined process such as the diffusion-limited growth process. The knowledge of the temperature dependence of the crystallization processes is of paramount importance for the processing of BMG forming alloys. It determines the repeatability and, thereby, the reliability that can be expected for a given processing method. The above ndings suggest that a reliable BMG processing method should be carried out at a temperature below the nose of the TTT diagram. In this SCLR temperature region both tonset and tcrystal are well dened and, thereby, repeatable, a core requirement for a robust, high-yield fabrication method. Another aspect for the development of such a fabrication process is the effect of heterogeneities on the crystallization. It has been observed that heterogeneities effect crystallization in the two regions in different ways,[93] which will be discussed in the following Section.

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Figure 4. TTT diagram for Pd43Ni10Cu27P20 processed while uxing in B2O3 (squares) or in absence of B2O3 (circles). In this diagram, the time to reach 1% (open), 50% (half open), and 95% (solid) crystallized volume fraction is shown as a function of temperature. Data points depict the average value of the performed experiments. Heterogeneous inuences have a signicant effect on crystallization at high temperatures but are negligible at low temperatures in the growth controlled region. Reproduced with permission from [93]. Copyright 2002, Taylor & Francis.

2.1. Heterogeneous Inuences on the Crystallization A major challenge in metal processing is that the vast majority of metallic melts are susceptible to oxidation. Even though other impurities in metallic melts can act as templates for heterogeneous nucleation sites, oxides are most ubiquitous among metallic melts. This occurrence is due to a generally high driving force for oxidation, the availability of oxygen during processing, and the signicantly higher melting temperature of the oxide compare to the metal. Nucleation on a template like an oxide is typically energetically favored over homogeneous nucleation (see, e.g., ref. [209]). The effect of heterogeneities on the crystallization can be quantied in the framework of classical nucleation theory (see, e.g., ref. [77]). Within heterogeneous nucleation, nuclei form on heterogeneities and use them as part of their own, depending on the wetting of the forming nucleus on the heterogeneity. In the extreme case the (effective) size of the heterogeneity exceeds the critical cluster size for nucleation, and nucleation is no longer required for the crystallization. As a consequence, crystallization kinetics are enhanced and the ability to form glass diminishes. For example, the processing conditions under which TTT diagrams are determined (listed in Table 1) are optimized to reduce/eliminate heterogeneous inuences on the crystallization process. When conditions deviate from ideal conditions to reduce heterogeneous inuences, crystallization kinetics are signicantly increased.[77,93,144,145,210218] Numerous efforts have been made to reduce heterogeneous inuences on the crystallization process. For example, the use of high-purity ingot material and processing in either (high) vacuum or an inert environment has been proven successful to reduce heterogeneous inuences.[93,218222] Research has also been focused on reducing oxide formation during processing and dissolving pre-existing oxides. A widely used strategy is the use of

boron oxide, B2O3. BMG formers for which B2O3 has been used as an effective ux to reduce oxides include FeB,[144] PdNiP,[211,223] PdNiCuP,[25,45,93,96,214,216,220,224,225] FeNiPB,[226,227] PtNiCuP,[51,62] and PdSi.[228] For these alloys, B2O3-ux treatment is very efcient to suppress, or at least reduce, heterogeneous nucleation (see, e.g., ref. [211]). In one example, the critical cooling rate of Pd43Ni10Cu43P20 was determined to 0.09 K s1 when processed in B2O3 ux and 0.4 K s1 when processed in its absence.[25] The efciency of uxing in B2O3 also reects in the largest reported casting thickness for a BMG former of 72 mm[225] and, when applying to small samples, the lowest critical cooling rate of 0.005 K s1 that has ever been measured for a BMG former.[220] A mechanistic understanding of the effect of B2O3 ux on the crystallization of PdNiCuP was gained from isothermal crystallization studies (Fig. 4[93]). It was found that the effect of B2O3 uxing is most pronounced in the nucleation-controlled high-temperature region (see Section 2). At low temperatures, on the other hand, where crystallization is growth controlled, B2O3 has a negligible effect on the crystallization kinetic. From microstructure analysis it was concluded that B2O3 passivates surface impurities and, thereby, suppresses surface nucleation.[93,144] The high efciency of B2O3 in this temperature region is due to the fact that in the nucleation controlled region the formation of only one nucleus is already sufcient to trigger crystallization. In the absence of B2O3 this typically occurs on a surface site.[27,144] At low temperatures, a large number of nuclei was found to be homogeneously distributed throughout the sample and to initiate crystallization. Therefore, the effect of B2O3 in this temperature region is negligible (see Fig. 4). The presence of B2O3 does only affect (a small number of) surface nuclei; the number is negligible compared to the number of nuclei that is formed within the sample. Hence, the presence of B2O3, does not

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noticeable change the crystallization kinetics in the growthcontrolled low-temperature region. The use of boron oxide as a ux is limited to alloys for which all their constituents have a lower heat of oxide formation than boron. This requirement excluded a wide range of BMG formers and stimulated the development of oxide reduction procedures that can be applied to other BMG formers. One such method is the use of an electrochemical method, where oxygen is removed from Zr-based BMG formers by direct electrochemical reduction in a molten-salt electrolyte.[229,230] For this purpose, an oxygen-containing cathode is submerged in molten CaCl2 or a eutectic mixture with other salts. When a current is applied, oxygen is ionized at the cathode, dissolved in the molten salt, and discharged as a gas at the anode. This reaction reduces the oxides in the BMG former and, thus, improves the glass-forming ability.[229,230] Yttrium was found to be efcient as an alloy addition to improve the glass forming ability in small volume fractions <5% for ZrCuNiAl alloys.[231] Similar effects have been achieved when adding scandium to ZrTiCuNiAl where smallest volume fractions of <0.06% as alloy additions are sufcient.[219] The effect of scandium reects in the critical casting thickness, which increases for ZrCuNiAlTi from 4.5 mm to 10 mm, when 0.06% of scandium is added to the alloy.[167] The effect of scandium on the glass-forming ability was explained by scandium oxide formation scavenging oxygen from other existing oxides in the material.[159] The effectiveness of this uxing indicates that scandium oxide(s) itself does (do) not act as an effective heterogeneous site.[232] Various other minor alloy additions were also found to improve the glass-forming ability of a wide range of BMG formers and are summarized in a recent review.[233] Taken together, although heterogeneous inuences are always present in a typical production environment, it appears that in the crystallization of BMG formers, the low-temperature region is less susceptible to heterogeneities. Therefore, fabrication processes should be developed that are based on low-temperature SCLR processing.

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Figure 5. Schematic TTT diagram illustrating the processing methods of BMG formers. 1) Direct casting: During direct casting forming takes place simultaneously with the required fast cooling to avoid crystallization. 2) TPF: During TPF the required fast cooling and forming are decoupled. The amorphous BMG is reheated into the SCLR, where the available processing window is much larger than during direct casting, resulting in better controllability of the process. After the forming processing step no fast cooling is required to avoid crystallization during cooling [81].

shown to lift the geometrical limitations imposed by the critical casting thickness, to provide better control, and to yield highest dimensional accuracy.

3.1. Direct Casting Casting methods such as suction and die casting have been used as BMG net-shape fabrication processes. The suction casting method yields high-quality parts with particularly low porosity[235] compare to samples prepared by die casting. A benet of die casting is, however, the ability to scale up to high-volume production of small- to medium-size articles. Currently, Liquidmetal Technologies are using die casting, which is adopted from conventional aluminum die casting for high-volume manufacturing of Zr-based BMGs (Fig. 6).[82] The typically low melting temperatures, which are summarized in Table 2 for some BMG formers, are benecial in a direct casting process because this process reduces tool costs and wear, lowers energy consumptions, and shortens cycle time. However, the critical cooling rate, dc, and the TTT diagram are signicantly affected by the maximum temperature prior to cooling. If this temperature does not exceed a threshold temperature, TOH, the glass-forming ability of the BMG former can be signicantly reduced. The existence of TOH, which is approximately 300 8C above the liquidus temperature of the BMG, has been reported for a variety of BMG formers.[94,189,212,218] In some BMG formers the overheating affects the viscosity.[16,94,189,212,218] This effect on viscosity may be explained by a variety of phenomena including melting of an oxide phase,[94,212] ordering phenomena,[16] and a chemical decomposition process.[189] The required overheating diminishes the processing benets of the low Tl of BMG formers. During suction casting as well as die-casting shrinkage has to be taken into consideration. Fortunately, the absence of a

3. Processing
One of the key requirements to advance new materials into a commercial usage is the development of robust, economic, and environmentally benign processing methods. In processing of BMGs the metastable nature of the amorphous state imposes the main challenge as any fabrication process must avoid crystallization during processing and solidication. Crystallization occurs when the cooling or heating path intersects with the crystallization curve of the TTT diagram (Fig. 5).[234] To circumvent such an intersection, the unique crystallization behavior among BMG formers permits two principally different processing paths. Path 1, in Figure 5, indicates the critical cooling rate for glass formation, the slowest cooling rate that avoids crystallization, and shows that a cooling rate such as path 1 or faster can be used for a casting process. During direct casting the forming takes place simultaneously with required fast cooling to avoid the crystallization nose. Path 2 represents the processing path for TPF.[81] Here, the required fast cooling and forming are decoupled, which will be

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Figure 6. Examples of commercially produced BMG articles using a diecasting method. Reproduced with permission from Otis Buchanan, Liquidmetal Technologies. Table 2. Thermophysical properties that are relevant for direct casting of selected BMG formers.
Alloy Zr41Ti14Cu12Ni10Be23 Zr57Nb5Cu15.4Ni12.6Al10 Au49Ag5.5Pd2.3Cu26.9Si16.3 Pt57.5Cu14.7Ni5.3P22.5 Ce68Al10Cu20Nb2 Fe48Cr15Mo14Er2C15B6 Tl [8C] 714 847 382 540 370 1190 TOH [8C] 950 $1020 $1000 Tcast [8C] $1000 4501100 700 1250 dc [mm] 25 12 5 16 8 12 Reference [16,28,94] [26] [48,189] [51] [50] [39]

BMG during the cooling process. The heat transport throughout the gap, which signicantly differs for a gap lled with a gas atmosphere or a vacuum, can become the rate-limiting factor, hence, can signicantly affect the cooling rate. Due to the crystallization mechanism and the crystallization kinetics in direct casting of BMG formers, fast cooling and forming has to be carried out simultaneously. Casting requires a careful balance of the cooling rate to assure mold lling while avoiding crystallization during solidication.[49,82] This is particularly challenging for the geometries in which BMGs express their full range of attractive properties. Furthermore, the intrinsic scatter in tonset (see Section 2) as well as the sensitivity of tonset to the processing conditions results in an unpredictable and fragile direct casting fabrication process. As a consequence, a low yield must be expected for BMG fabrication processes based on direct casting. Table 3 summarizes the advantages and disadvantages of processing methods based on direct casting.

REVIEW

3.2. Thermoplastic Forming An alternative processing method to direct casting of BMGs, unique among metals, is TPF, where forming and cooling to render the amorphous state during solidication are decoupled (Fig. 5). The process is also known as hot forming,[238] hot pressing,[239] super plastic forming,[81] viscous ow working,[117] and viscous ow forming.[240] TPF takes advantage of the drastic softening of the BMG former upon heating above Tg and its thermal stability. The thermal stability is a measure of the ability of BMG formers to retain an amorphous structure when heated above its glass-transition temperature and is quantied by the width of the SCLR. During TPF, the BMG is reheated into the SCLR, where it relaxes into a supercooled and metastable liquid before it eventually crystallizes. An example of the temperature dependence of the crystallization time and viscosity for Zr44Ti11Cu10Ni10Be25 is shown in Figure 7. At low temperatures a long processing time is available for Zr44Ti11Cu10Ni10Be25, accompanied by a high viscosity. At high temperatures, on the other hand, the viscosity is signicantly reduced but, at the same time, the processing time is shortened. For a variety of BMG formers a large processing window exists,[241] which permits access to temperatures in this region on

rst-order phase transition during solidication reduces solidication shrinkage in BMG formers drastically. Phase-transition shrinkage of about 5% is typical for casting alloys.[236] The solidication shrinkage during casting of a Zr-based BMG former, in comparison, is approximately only 0.5%.[81] The one order of magnitude reduction in solidication shrinkage of BMG formers over conventional casting alloys suggest a much higher dimensional accuracy in casting of BMG. It has also been observed that the casting environment is crucial to the cooling process.[237] Even the low solidication shrinkage in BMG formers creates a gap between the mold and

Table 3. Advantages and disadvantages of direct casting of BMGs.


Advantages of Direct Casting Low melting temperature Low shrinkage Comment Disadvantages of Direct Casting Comment Metastable nature of BMG required fast cooling Most BMGs are reactive and vacuum/inert conditions are required; Costly high purity ingot materials The low uidity of BMG liquids makes casting more difcult The required fast cooling results in internal stresses Limited reusability of material

Composition close to eutectic composition Cooling and forming are coupled Absence of rst-order phase Processing environment can inuence transition during solidication crystallization kinetic High viscosity Internal stresses

One-step process No directional growth, no crystals, no intrinsic size limitation Mechanical properties are already No subsequent heat treatment mature in the as-cast state Homogeneous microstructure

BMGs contaminate during processing[a] $300 8C overheating above Tl required Diminishes the benets of a low Tl

[a] For some BMG compositions a ux can be used, which reduces contamination (see Section 2.1).

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the modeling of the lling of a cylindrical mold assuming creeping ow conditions.[81] In this approach, stick conditions are assumed, i.e., zero velocity of the liquid at the channel/liquid interface and a Reynolds number of $0. Under these conditions, the formability of a BMG in the SCLR can be quantied using the HagenPoiseuille Equation (1):

REVIEW

p 32v h

L d2

(1)

where p is the required pressure to move a liquid with viscosity, h, at a velocity, v, through a channel of thickness d and length L. The maximum time available for the forming process is limited by tonset. Substituting v L/tonset in Equation (1) gives for the maximum length that can be lled:

s p tonset d2 L 32h

(2)

Figure 7. A) TTT diagram, indicating tonset and the temperature-dependent viscosity for Zr44Ti11Cu10Ni10Be25. Reproduced with permission from [120]. Copyright 2003, American Institute of Physics. B) Filling length as a measure for the isothermal formability [81], calculated according to Equation (2) with parameters shown in (A) and p d 1. Reproduced with permission from [245]. Copyright 2007, IEEE.

a practical experimental time scale. The onset of crystallization, the upper bound of the SCLR, is usually determined through thermal analysis by detecting the heat of crystallization. Alternatively, it can also be detected from ow-stress measurements where the onset of crystallization is indicated by a sharp rise in the ow stress.[81] The ability to access such low viscosities on an experimentally practical time scale allows us to process some BMG formers similarly to plastics.[82] Today, for a wide range of alloys, viscosities of 106 Pa s and lower can be accessed in the SCLR on a practical time scale.[17,84,87,118,120,242,243] For the highest formability of the BMG former in its SCLR, optimum processing parameters such as low viscosity and long processing time are required. The formability is a material property that reects the maximum strain a metastable material can undergo before it crystallizes under given geometry and processing parameters. Despite the early recognition[244] and utilization[238] of TPF-based processes for net-shaping, methods for the characterization of a formability of BMG were not developed until very recently. One method to determine the processing parameters, which results in highest formability of the BMG in its SCLR, is

This lling length can be used to quantify the isothermal formability of BMGs in their SCLR. The formability depends on the viscosity and the lling time given by tonset. An example of the temperature-dependent isothermal formability, characterized by the lling length, is shown in Figure 7. In this gure, the lling length shown in Figure 7B was calculated for Zr44Ti11Cu10Ni10Be25 using the parameters shown in Figure 7A and a typical forming pressure of 100 MPa.[81] The calculated lling length continuously increases with increasing temperature. This temperature dependence of the formability can be contributed to the stronger temperature dependence of the viscosity than that of tonset (see Fig. 7A). This nding suggests that in order to maximize thermoplastic formability of BMGs, the highest possible temperature should be chosen, while avoiding crystallization during the forming process.[81] However, the above described method to determine processing conditions that result in the highest formability is not suited as a method to determine the formability of BMG formers because it requires impractical molds with highest aspect ratio. Therefore, in the past, the smallest feature that could be replicated was often taken as a measure for a BMGs formability (see, e.g., ref. [246]). Other methods were developed to quantify the formability of BMGs. As the maximum strain that a metastable material can undergo depending on the geometry and processing parameters, the formability should be measured in a dened geometry under dened processing parameters. Under the assumption of Newtonian behavior, i.e.,

_ s h 3"

(3)

_ where s is the ow stress and " the strain rate, and under isothermal conditions, the maximum strain, emax, can be calculated by integrating Equation (3) between 0 and tonset:
tonset Z 0

_ "dt

s dt 3h

(4)

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Thus, the maximum strain achievable under isothermal conditions is given by:

"max tonset

s 3h

(5)

Here, the quantity reecting the isothermal formability, F, is:

tonset 3h

(6)

correlation between d and the considered parameters was found between d and S, followed by the one between d and mDT/Tg. The weakest correlations were found between d and Tg/Tl and between d and DT. In addition, to show the best correlation with the experimentally determined formability, the parameter S possesses a signicant practical advantage. It solely requires thermophysical data that can be determined from a differential scanning calorimetry (DSC) thermogram. Based on these ndings, we conclude that thermophysical properties that indicating good formability of a BMG former are: fragile liquid behavior, large Poisson ratio, and a low glass transition. 3.2.1. The Effect of TPF on the Mechanical Properties of BMG FormersEmbrittlement The temperature exposure during TPF-based processing has been a concern as it may cause (thermal) embrittlement, the degradation of mechanical properties due to thermal exposure. The effect of annealing on embrittlement has been studied for a number of metallic glasses, including Fe-based,[251,252] Zr-based,[253,254] La-based,[255] and Mg-based[256,257] alloys. Thermal embrittlement of BMGs is controversial and has been attributed to a wide range of phenomena such as structural relaxation and free volume annihilation,[253,254,258263] crystallization,[264267] phase separation,[261,268] residual stresses,[252] and short-range ordering.[269,270] Recent comprehensive work has suggested different origins for the thermal embrittlement during annealing temperatures above and below the glass transition.[271] Embrittlement due to annealing below Tg originates from structural relaxation. Above Tg on the other hand, crystallization causes annealing induced embrittlement.[271] These conclusions were drawn from a comparison of the time scales for structural relaxation, crystallization, and embrittlement (Fig. 9). However, it has also been shown that annealing below Tg for only a fraction of the total relaxation time is already sufcient to signicantly embrittle the material.[271] Structural relaxation can be described in the framework of the potential energy landscape model. Within this concept, the structural congurations of a glass are represented by local minima in a potential energy landscape.[272,273] The transition of the undercooled liquid into a glass corresponds to trapping the conguration into local minima within a mega basin. Some minima in the mega basin are separated by small energy barriers, and changing the conguration between these minima involves local rearrangements of a small number of atoms, called beta-relaxation. Mega basins are separated by large energy barriers and, thus, a transition from one mega basin to another requires a global cooperative rearrangement of atoms, known as alpha relaxation. The structural relaxation or viscosity relaxation described by the VogelFulcherTamman (VFT) equation is related to these alpha-relaxation processes, which are causing the BMG to embrittle. Macroscopically, this relaxation results in an increase of density or, in other words, a decrease of free volume.[274] The relaxation processes described above are accompanied by signicant changes in physical properties of the metallic glass. One practical issue is the severe embrittlement observed through fracture toughness, impact toughness, and bending ductility measurements.[254,264] Annealing also affects the elastic constants

REVIEW

The formability parameter can be extended to constant heating conditions by modifying Equation (4) and (2):
_ Tx T

1 _ 3T

1 dT h T

(7)

Tg

where Tx is the heating-rate-dependent crystallization temperature. Equation (6) reveals the strong temperature dependence of the formability. The viscosity of a BMG changes roughly by one order of magnitude every 20 K, while the crystallization time changes by an order of magnitude every 50 K.[120] For example, an error of 10 K in the temperature measurement would result in an error of 40% in F according to Equation (6). Because precise temperature control is experimentally challenging to establish, a practical method to characterize the formability must be less temperature sensitive. One approach is to characterize the formability during constant heating as described by Equation (7). However, in order to calculate F(T) according to Equation (7), elaborate measurements of h(T) and _ Tx Tare required. Therefore, Equation (7) does not offer a practical quantity to determine the formability of BMGs. A recently introduced practical method to quantify the formability of BMGs approximates F(T) well, according to Equation (7).[241] Within this method, standard conditions are dened.[241] The formability is reected in the nal diameter, d, to which the BMG deforms under the following conditions: a sample volume of 0.1 cm3, a constant load of 4500 N, and a constant heating rate of 20 K min1 applied in the temperature range between Tg and Tx. This set of parameters results in the best combination of accuracy and practicality in determining the formability of a BMG. The formabilities of ten different BMGs are depicted in Figure 8 and results are summarized in Table 4. By far the largest formability, reected in the largest d value was measured for Pt57.5Cu14.7Ni5.3P22.5, followed by Zr35Ti30Be27.5Cu7.5, and Pd43Ni10Cu27P20. These data were used to test the correlation with parameters, some of which where used in the past to indicate the formability, including Tg/Tl, DT, DT/Tg, mDT/Tg (m is steepness index),[247] S DT/(Tl Tg), and Tg. Figure 8BH depicts F (B), Tg/Tl (C), Tg (D), DT (E), DT/Tg (F), mDT/Tg (G), and S (H), which are plotted against the experimentally determined formability, d. Also shown in Figure 8B is the formability, which has been calculated according to Equation (7) with parameters shown in Table 4. The strongest

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REVIEW
Figure 8. A) Top view of the various BMGs after the formability characterization evaluation. All samples are deformed until they crystallize and the maximum diameter is a measure for BM6s formability. 1) Zr44Ti11Cu10Ni10Be25, 2) Zr57Nb5Cu15.4Ni12.6Al10, 3) Zr58.5Nb2.8Ni12.8Cu15.6Al10.3, 4) Pt57.5Cu14.7Ni5.3P22.5, 5) Zr41Ti14Cu12Ni10Be23, 6) Au49Ag5.5Pd2.3Cu26.9Si16.3, 7) Pd43Ni10Cu27P20, 8) Zr65Al10Ni10Cu15, 9) Mg65Cu25Y10, and 10) Fe48Cr15Mo14Er2C15B6. BH) Correlation between experimentally determined formability, d, and various parameters: F (B), Tg/Tl (C), Tg (D), DT (E), DT/Tg (F), mDT/Tg (G), and S (H). Pd43Ni10Cu27P20 ( ), Mg65Cu25Y10 ( ), Fe48Cr15Mo14Er2C15B6 ( ), Au49Ag5.5Pd2.3Cu26.9Si16.3 ( ), Zr57Nb5Cu15.4Ni12.6Al10 ( ), Zr58.5Nb2.8Ni12.8Cu15.6Al10.3 ( ), Zr65Al10Ni10Cu15 ( ), Zr41Ti14Cu12Ni10Be23 ( ), Zr44Ti11Cu10Ni10Be25 ( ), and Pt57.5Cu14.7Ni5.3P22.5 ( ). Reproduced with permission from [241]. Copyright 2008, Elsevier.

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www.advmat.de www.MaterialsViews.com Table 4. Summary of the parameters and formability for various BMG formers.
Alloy Zr41.2Ti13.8Cu12.5Ni10Be22.5 Zr44Ti11Cu10Ni10Be25 Zr35Ti30Be27.5Cu7.5 Zr57Nb5Cu15.4Ni12.6Al10 Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Pd43Ni10Cu27P20 Au49Ag5.5Pd2.3Cu26.9Si16.3 Pt57.5Cu14.7Ni5.3P22.5 Fe48Cr15Mo14Er2C15B6 Mg65Cu25Y10 Zr65Al10Ni10Cu15 Ca65Li14.54Mg12.46Zn8 Ce70Al10Cu20 Tg [8C] 349 350 301[c] 405 400 305 130 236 573 155 368 35 68 Tx [8C] 426 471 467 470 480 406 184 325 620 219 473 105 135 DT [8C] 77 121 166 65 80 101 54 89 47 64 105 70 67 Tl [8C] 714 720 798 847 845 554 382 540 1190 484 888 341 449 m 47.9 47.2 45.9 45.9 65.2[e] 52.8 51.9 42.7 59.4 D* 23.8[a] 18.9[b] 19.7[d] 19.7[d] 12 16[f ] 16.4[g] 22.1[h] 16.6[i] To [8C] 117 117 164 164 92 23 63 13 164 y 0.352 0.349 0.379 0.377 0.396 0.406 0.43 0.32 0.305 0.377 S 0.21 0.33 0.33[c] 0.15 0.12 0.41 0.21 0.29 0.08 0.19 0.2 0.23[j] 0.18[k] F [Pa1] 2.2 10 3.5 104 1.5 107 4 107 1.1 105 9.9 104 2.1 104 3.8 106 1.9 105
7

REVIEW

d 14.1 20.5 27 11.2 14.65 25.55 21.56 32.7 6.2 17.9 13.6

[a] Ref. [122]. [b] Ref. [120]. [c] Ref. [243]. [d] Ref. [248]. [e] Ref. [118]. [f ] Ref. [49]. [g] Ref. [242]. [h] Ref. [249]. [i] Ref. [250]. [j] Ref. [52]. [k] Ref. [50].

of metallic glasses.[275278] Recently, the plasticity or brittleness of as-cast and annealed metallic glasses has been correlated with Poissons ratio n (or the ratio m/B, where m is the shear modulus and B the bulk modulus).[62,279] It has been suggested that a critical value of n of less than 0.32 (or m/B > 0.41) predicts a transition from tough to brittle behavior in metallic glasses.[256,279] Recent annealing studies,[271] however, do not support this suggestion. In this work, even though the elastic constants show a clear trend during embrittlement of BMGs, the values of n and m/B during (severe) annealing-induced embrittlement remain well above and below the respective critical values. These contradictive ndings might suggest that in order to quantify the toughness or brittleness of metallic glasses, criteria beyond the Poisson ratio have to be considered. Crystallization during annealing above Tg also affects the viscosity of the BMG formers.[281,282] Compression testing of partially crystallized Zr41.2Ti13.8Cu12.5Ni10Be22.5 suggest that the increase in ow stress cannot be interpreted through a

compositional change in the residual amorphous matrix but is due to the nanometric size of the crystals.[281] The tendency to embrittle during (service) temperature exposure limits the service temperature BMGs can be used at. In particular for longer exposures, the service-temperature range must be signicantly reduced to a value below its glass-transition temperature to avoid thermal embrittlement of the BMG former. Fabrication of BMG articles by TPF-based processing, on the other hand, does not cause embrittlement, as long as crystallization is avoided.[271]

3.3. Fabrication Processes Based on Thermoplastic Forming The ability to thermoplastically form BMGs in their SCLR is unique among metals. This process is based on the dramatic softening of the BMG former when heated into the SCLR (see Section 3.2). The glass-transition temperature and the softening in the SCLR permits the use of processing temperature and pressure that, for some BMGs, are comparable to those of plastics.[82] Therefore, processing methods developed for the processing of (thermo) plastics are often more appropriate than metal processing techniques as inspirations for the development of processing methods for BMGs. The ability to plastically form metallic glasses in the vicinity of Tg was recognized[244] and demonstrated,[238] already in the early days of metallic-glass research. But it was the recent development of BMGs with enhanced formability[4548,50,51,117,283] that accelerated the development of a wide range of processing methods based on thermoplastic forming. All these processes have in common that an amorphous BMG feedstock is used. The form and shape of this feedstock can vary from powder[49,81,284] over rods,[285] disks,[286] plates,[82,287] and lms[288290] to preshaped parisons.[291] However, ubiquitous among all the feedstocks is their ease to cast (or deposit) shape using standard methods. Forming of the feedstock material takes place in a subsequent processing step at a temperature in the SCLR where the forming pressure exceeds the ow stress of the BMG. The ow stress depends on

Figure 9. A schematic illustration of the embrittlement kinetics in BMG formers. Below Tg, structural relaxation is the origin for annealing embrittlement of BMGs whereas above Tg crystallization causes embrittlement. Reproduced with permission from [271]. Copyright 2009, Elsevier.

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Advantages of TPF-Based Processing Comment Disadvantages of TPF-Based Processing Two- or more-step process Comment

REVIEW

Forming and fast cooling decoupled Highest dimensional accuracy Insensitive to heterogeneous inuences Novel and unique process green process Low capital investment

Wide range of complex shapes can be net-shaped Due to negligible stresses and negligible solidication shrinkage Predictable and robust process Allows to process in air New opportunities Due to low processing temperature and pressure, ability to net-shaping Also allows small series and custom shaped parts

A requirement from the decoupling of cooling and forming

Novel and unique process

Requires the development of novel processing methods

the strain rate, which itself is given by the required strain on a time scale limited by the crystallization. Generally, TPF of BMGs can be carried out in air.[81] This reects in the insensitivity to heterogeneous effects on the crystallization in the SCLR (see Chapter 2.1). Furthermore, the available processing time for TPF is well determined and thereby reproducible, a basic requirement for a robust and high-yield manufacturing process. The option of slow cooling after the forming process can be used to essentially eliminate internal stresses, whereby high dimensional accuracy in complex geometries can be achieved. A summary of the TPF-based processing advantages and disadvantages is given in Table 5. They motivated: the development of BMGs specically designed for TPF processing and the development of TPF-based processing methods. These TPF-based processing methods can be categorized into groups, as described in the following section. 3.3.1. TPF-Based Compression and Injection Molding with BMGs Compression molding as a net shaping method for BMGs was adopted form plastic processing. Within compression molding the BMG feedstock material is placed in a mold and heated into the SCLR, where a pressure is applied that must exceed the ow stress of the BMG to achieve the required strain before crystallization sets in. No fast cooling is required after forming.[81] A schematic image of the process, together with examples, is shown in Figure 10. TPF-based processes can be used as net-shape fabrication methods for BMGs.[117] Initial focus was on relatively simple features in the 500-mm range and on PdNiCuP, a BMG with excellent formability. Under low applied pressure, this alloy can be formed into gear-shaped geometries. Subsequently, particles of approximately 1-mm diameter of Pt57.5Cu14.7Ni5.3P22.5 BMG[81] and Au49Ag5.5Pd2.3Cu26.9Si16.3[49] were used as a feedstock for compression molding. It could be shown that a dense compact part with

mechanical properties close to those of the bulk material and an excellent surface nish can be obtained. Figure 10 shows compression molding of BM6 former, where different feedstock shapes such as pellets (B) of Pt57.5Cu14.7Ni5.3P22.5, as well as plates (C) and rods (D) of Zr44Ti11Cu10Ni10Be25 have been used. The required molding pressure depends not only on the formability of the BMG at the processing temperature but also strongly on the shape of the nal part. For example, the part shown in Figure 10D is 3 mm thick, compared to 1 mm of the part shown in Figure 10C with similar lateral dimensions. Consequently, the forming pressure, which is required to mold the structure shown in Figure 10D is 20 MPa compared to 250 MPa for the structure shown in Figure 10C. Injection molding was also developed as a TPF-based process to net-shape BMG formers.[292] Principally, injection molding and

Figure 10. TPF-based compression molding with BMG. A) Schematic images of compression molding with BMGs. B) Pellets used as feedstock material to compression mold Pt57.5Cu14.7Ni5.3P22.5. Reproduced with permission from [49]. Copyright 2007, Elsevier. C) Zr44Ti11Cu10Ni10Be25 formed from a at plate into a corrugated structure. D) Zr44Ti11Cu10Ni10Be25 formed from a at plate to create an embossing mold.

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compression molding are similar in their achievable geometries and processing parameters. In contrast to compression molding, within injection molding, the feedstock material is translated into the mold cavity, which can be advantageous for the development of commercial fabrication processes with minimized cycle time. 3.3.2. Miniature Fabrication Advancements in technologies such as micro-electromechanical systems (MEMS), electronics devices, and medical devices have created an increasing demand for miniature parts and components on the length scale of micrometers to centimeters. A currently used miniature-fabrication method is LIGA, a German acronym that stands for lithography, electroplating, and molding. It provides on-demand manufacturing of high-aspect-ratio structures with a lateral precision of less than one micrometer.[293] LIGA allows a variety of geometries to be manufactured on length scales ranging from about 10 mm up to about 1 mm.[293] The use of electroplating within LIGA techniques, however, limits the range of materials that can be used. But the main drawback of LIGA is its cost: high-energy X-rays generated by synchrotron facilities are required to expose the thick poly(methyl methacrylate) (PMMA, an acrylic glass) resists. A more economical alternative is UV-LIGA, in which UV light is used to expose a thick layer of photoresist.[294] Geometries similar to those created by LIGA, but with limited precision, can be achieved using UV-LIGA. Both processes are typically used as surface-patterning techniques for creating high-aspect-ratio structures but precise plating can also create free-standing 3D parts. The homogeneous and isotropic structure of BMGs down to the atomic scale, their superior properties over conventional materials used for miniature applications, and the ability to fabricate stress-free parts has triggered signicant effort to develop BMG miniature-fabrication methods. A schematic image of miniature forming based on TPF of BMGs is shown in Figure 11A. Molds of various materials have been used, where the most common are silicon molds prepared by lithography. Miniature forming is performed under conditions as described above for (macroscopic) molding. Typically, after miniature forming, the mold is dissolved to release the formed BMG miniature part (see Fig. 11A,i). Saotome et al. pioneered miniature fabrication of BMGs through TPF and used ZrNiCuAl,[296] PtPd-based,[297299] and La-based alloys.[300] Inspired by this work, a wide range of geometries and features, as small as 250 nm, were fabricated by other groups. This approach has also been extended to BMGs with particularly high formability such as Zr44Ti11Cu10Ni10Be25, Pt57.5Cu14.7Ni5.3P22.5, and Au49Ag5.5Pd2.3Cu26.9Si16.3 to fabricate under highest precision high-aspect-ratio features.[49,81,82,301] Miniature forming based on TPF as described in Figure 11A,i was applied for various geometries,[302] particular applications,[303] and a variety of BMG alloys.[304,305] Figure 11B shows some examples of surface replication, which were fabricated according to the method described in Figure 11A,i. Potential applications include mold application for a variety of imprint processes.[81,245,280,296,303] In addition, patterned surfaces can be fabricated,[291] which includes programming desirable cell response through surface patterning when using BMG in the human body.[306]

Ubiquitous among all the above mentioned fabrication methods is that a TPF process is used to replicate features from a mold to the surface of a BMG. To create 3D parts, these features have to be separated from the forming reservoir. Standard machining techniques like cutting and grinding are challenged at these dimensions because their accuracy is often comparable with the actual size of the miniature part.[307] An alternative approach makes use of the thermoplastic formability of BMGs where the reservoir is separated from the features through a scrapping process, carried out at a temperature in the SCLR (Fig. 11A,ii).[245] This scraping results in a smooth and precise separation between the miniature part and the reservoir. By combining the TPF-based surface replication (embossing) together with the hot-scrapping techniques, 3D miniature parts can be fabricated at highest precision. Some examples of 3D parts fabricated by embossing and scrapping are shown in Figure 11C. Often, the majority of the processing cost of a miniature part is consumed by the cost to fabricate a mold. In particular, precision mold making on the miniature length scale is challenging and expensive. Even deep reactive ion etching (DRIE) of silicon typically leaves scallops, a surface roughness of about 300 nm (see, e.g., ref. [308]). Even a slight improvement of the surface nish of miniature molds is laborious and expensive.[309,310] Therefore, in order to develop an economic miniature-fabrication process, Kumar et al. proposed a method to smoothen BMG surfaces on intricate BMG miniature parts in a subsequent processing step after being released from the mold.[295] They found that for some BMG former the viscosity in the SCLR is sufciently low that the action of the surface tension alone generates viscous ow to smoothen the roughness of BMG parts on a time scale before crystallization sets in.[295] Figure 11d shows the smoothening of a pyramid shaped feature imprinted on Pt57.5Cu14.7Ni5.3P22.5 during annealing at 270 8C. The onset of crystallization for this alloy at 270 8C is 1200 sec but already after 300 sec the imprinted feature is almost completely eliminated. Kumar et al. [295] also developed a theoretical description for the erasing time of surface perturbations:

REVIEW

te

9hh0 g

(8)

where h0 is the initial height of the feature and g the liquidvacuum surface energy. One application of this surfacetension-driven viscous ow is to smoothen the surface on complex miniature parts (Fig. 11D). Thereby, inexpensive molds with rough surfaces can be used within the fabrication process and the surface of the BMG part is smoothened in a subsequent processing step. Equation (8) suggests that the range of geometries is limited to a surface roughness, which is small compared to a typical dimension in the part, in order to combine highest accuracy and a smooth surface nish. If they become comparable, the shape itself will also be affected by the annealing and, thereby, the dimensional accuracy sacriced. 3.3.3. BMG as a Mold Material Since in miniature- and nano-fabrication methods a signicant fraction of the costs is consumed by the synthesis of the mold,

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Figure 11. A) Schematic image of the miniature-fabrication process based on thermoplastic forming of BMG. Surface replication (embossing, (i)) and combination with hot-scraping (ii) to result in free-standing 3D parts [245]. Reproduce with permission from [245]. Copyright 2007, IEEE. B) Examples of surface replication (embossing) on the miniature length scale (millimeter to micrometer). C) Examples of 3D BMG miniature parts fabricated by process (ii). Reproduced with permission from [280]. Copyright 2009, Nature Publishing Group. D) Surface smoothening of BMG in the SCLR solely under the action of the surface tension. Reproduced with permission from [295]. Copyright 2009, American Institute of Physics.

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particularly when disposable molds are used,[308] BMG technology has been explored for mold application. The requirements for a material to be used as a mold are high strength and hardness combined with economic and precise fabrication ability. These requirements are fullled when BMGs are used at a temperature signicantly below their Tg, where they exhibit high strength and hardness. Figure 12A compares the temperature-dependent strength of selected BMGs with PMMA, a typical imprint material, and with various mold materials. At temperatures below their Tg, BMGs have characteristics desirable for mold application. At a temperature above Tg, some BMGs exhibit a ow stress comparable to those present in polymers.[82] Thus, BMGs can be considered a high-strength material that can be processed like a plastic. Figure 12A shows the ability to use a BMG as a hard mold material at ambient temperatures (below Tg) and as a soft moldable material at elevated temperatures. This unique feature stems from the highly non-linear softening of BMGs when approaching Tg.[311,312] This feature is due to the crossover in time scales of the internal relaxation time and the external experimental time. The internal time scale is dened by the Maxwell relaxation time, tmax h/G, where G is the shear modulus. The external time scale is dened, for example, by the strain or cooling rate. Fabrication of the mold can be accomplished using TPF-based compression molding. The interchangeable usage of BMGs as mold or as a moldable material can even be used to replicate one BMG mold with another BMG, as long as the BMGs have different softening temperatures. This was demonstrated by using a sequence of BMG formers with decreasing Tgs, Zr44Ti11Cu10Ni10Be25 (Tg 350 8C), Pt57.5Cu14.7Ni5.3P22.5 (Tg 228 8C), and Au49Ag5.5Pd2.3Cu26.9Si16.3 (Tg 128 8C), as shown in Figure 12BE. A nickel master shown in Figure 12B is replicated at 450 8C for 100 s under a pressure of 10 MPa with Zr44Ti11Cu10Ni10Be25, (Fig. 12C). In this processing step, the BMG is used as the imprint material. This structure is then used as a mold for Pt57.5Cu14.7Ni5.3P22.5. Perfect replication is achieved when processed at 280 8C for 50 s under a pressure of 10 MPa (Fig. 12D). Here Zr44Ti11Cu10Ni10Be25 is used as a mold and Pt57.5Cu14.7Ni5.3P22.5 as the imprint material. A BMG with an even lower Tg is used to replicate the Pt57.5Cu14.7Ni5.3P22.5 structure. Au49Ag5.5Pd2.3Cu26.9Si16.3 is processed at 160 8C for 50 s under a pressure of 10 MPa (Fig. 12E) and a perfect replication of the Pt57.5Cu14.7Ni5.3P22.5 mold can be achieved. The above demonstrates a precise and economic method to create a mold that possesses high strength and durability when used at a service temperature below its glass-transition temperature. Utilizing the highly non-linear temperature dependence of the softening of BMGs provides a versatile toolbox for imprinting, particularly when sequential master daughtergrand daughter mold replications are required.[245,280] 3.3.4. Nanoforming BMGs have many attractive characteristics for top-down nanofabrication. Among them are their homogeneous structure on the nanometer scale (<100 nm), the low required forming pressure and temperature, and their superior mechanical properties. For example, TPF-based processing techniques can be used to imprint Pd40Ni20Cu20P20 BMG into V-groove shapes, which are prepared by electron-beam lithography and anisotropic

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Figure 12. Temperature-dependent strength of materials used for molds and imprints for micro- and nanoimprinting. Silicon, quartz, and alumina exhibit strengths above 1000 MPa, making them suitable for use as mold materials. The strength of BMGs above Tg is calculated from their viscosity values by assuming Newtonian behavior (s 3he) and a strain rate, e, of 102 s1. Reproduced with permission from [280]. Copyright 2009, Nature Publishing Group. BE) The highly non-linear softening of BMGs (A) permits sequential use of BMG as mold or imprint material. C) Zr44Ti11Cu10Ni10Be25 with Tg 350 8C, D) Pt57.5Cu14.7Ni5.3P22.5 with Tg 228 8C, and E) Au49Ag5.5Pd2.3Cu26.9Si16.3 with Tg 128 8C. The nickel master (B) is replicated at 450 8C for 100 s under a pressure of 10 MPa with Zr44Ti11Cu10Ni10Be25 resulting in (C). This structure is then used as a mold for Pt57.5Cu14.7Ni5.3P22.5. Perfect replication is achieved when imprinted at 280 8C for 50 s under a pressure of 10 MPa as shown in (D). Finally, Au49Ag5.5Pd2.3Cu26.9Si16.3 is imprinted at 160 8C for 50 s under a pressure of 10 MPa (E) to replicate (D). Reproduced with permission from [245]. Copyright 2007, IEEE.

etching with a minimal width of 200 nm. Using the owed area into the groove, the ability of Pd40Ni20Cu20P20 to ll submicrometer features[297] and also the effect of processing parameters, such as the lling time on the formability, can be determined.[298]

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500-nm features on Mg-based BMG using a patterned nickel mold were formed[313] and the nanoformability of ZrCuNiAl BMG using nanocrystals of ZnMnO as a die material[290] were explored. Despite the large number of studies on the formability of BMGs on the submicrometer length scale, evidence for nanoimprinting with BMGs has been rare. Very recently, it has been suggested that on the nanometer scale the forming of BMGs is not primarily controlled by the viscosity but, instead, by the capillary forces.[280] Consequently, for the forming pressure:

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  32h l 2 4g cos u t d d

(9)

where g is the BMG-vacuum interfacial energy ($1 Nm1)[314] and u is the dynamic contact angle between the supercooled liquid and the mold. As an example, Equation (9) is plotted in Figure 13 for typical parameters: aspect ratio l/d 3, h 107 Pa s, t 60 s, and g 1 N m1. Under typical forming conditions the capillary term (second term in Eq. (9)) can become comparable with the viscous term for features of about 100 nm in diameter. However, whether the capillary term retards or facilitates the lling depends on the wetting conditions between the BMG and the mold. Ideal processing conditions require a (positive) forming pressure of about 50 MPa. A higher forming pressure is impractical with most potential molds. A low or even negative forming pressure renders the forming process uncontrollable and imposes challenges to the mold release. Experiments to determine the wetting angle between BMG and potential mold materials have revealed a wide range of wetting behaviors.[315] Pt57.5Cu14.7Ni5.3P22.5 and Al2O3 have been identied as candidates for BMGmold combination with desired wetting conditions.[280] With this combination, the molding on the nanometer scale can be precisely controlled where features as small as 13 nm have been formed.[280] Some examples of nanometer-scale features formed using Pt57.5Cu14.7Ni5.3P22.5 and Al2O3 are shown in Figure 14. Currently different material classes are used as the mold and imprint material[316] for nanoimprinting (Fig. 12A).[280] Silicon, quartz, and alumina exhibit strengths above 1000 MPa, making them suitable for use as mold materials. PMMA is a common imprint material due to its low forming pressure at temperatures above its Tg. BMG former cover a wide range of (temperature dependent) strength from ideal mold to imprint material (Fig. 12A). Thereby, BMGs are high-strength materials below their respective Tg, yet soft and moldable in the SCLR. This characteristic suggests that they might be well suited for the use as both mold as well as imprint material in a combination with other material classes or even with other BMGs as demonstrated in Figure 12BE.[245] The high strength at room temperature combined with additional desirable mechanical properties, the ability to imprint nanometer-size features in a parallel print process, the highly non-linear softening of BMGs when approaching their glass transition, and the ability to repeatedly write and erase features on the BMG surface suggest a wide range of application in nanofabrication. One such application is nanoimprint lithography ( NIL), a high-resolution and high-throughput

Figure 13. Molding pressure required to ll a channel of diameter d with aspect ratio of 3 with a supercooled liquid for antiwetting (u > 908) and wetting (u < 908) conditions [280]. The values used for viscosity, surface tension, and lling time are 107 Pa s, 1 Nm1, and 60 s, respectively. For complete antiwetting (u 1808), the required pressure becomes enormously high due to opposing capillary pressures (see Eq. (9)). Complete wetting (u 08) of a supercooled liquid result in spontaneous lling of the mold features by capillary action. However, the partially wetting supercooled liquid permits better control over the process as marked by desired molding region. Reproduced with permission from [280]. Copyright 2009, Nature Publishing Group.

thermomechanical manufacturing process, where a nanostructured mold is pressed into a thermoplastic polymer (such as PMMA) at elevated temperature, resulting in a negative replica of the mold in the polymer.[317,318] The high throughput offers an economical alternative to standard silicon-based fabrication technologies for nanoelectronics and nanoelectromechanical systems. The success and proliferation of NIL critically relies on the manufacturing of robust and durable master and/or daughter molds.[318] Silicon-based molds are brittle[319] and have limited longevity.[320] Metal molds are stronger than semiconductors but patterning of metals on the nanometer scale is limited by their nite grain size. Nanoimprinting with BMGs might be used to replicate the fragile and expensive master Si mold into a BMG. This BMG daughter mold would than be used as a robust and long-lasting working mold to imprint into the thermoplastic polymer. Nanoimprinting on BMG allows also to directly write, for example, with an atomic force microscopy (AFM) tip, as in a scanning probe lithography process (see, e.g., ref. [316]). The ability of some BMGs for direct nanoimprinting on the nanometer scale can be combined with the surface-smoothening method[295] and used as a rewritable high-density data-storage technique. For example, according to Equation (8), (13)-nm features can be written and erased about 1000 times before crystallization eventually sets in.[280] Either parallel or sequential direct writing on the nanometer scale onto a BMG can be used for the fabrication of lithography masks. An enhanced resolution over currently used chromium masks may be feasible, as demonstrated through focus ion beam (FIB) writing into a BMG.[290]

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Figure 15. Image of an extruded Zr44Ti11Cu10Ni10Be25 wire, 2 mm in diameter. Extrusion took place through a die with theoretical zero effective length under a ram pressure of 400 MPa. Reproduced with permission from [333]. Copyright 2009, Elsevier.

Figure 14. Nanoimprinting of Pt57.5Cu14.7Ni5.3P22.5 using porous alumina as a mold. The glassy rods of diameters13 nm (a) and 35 nm (b) with aspect ratios exceeding 50 were formed when Pt57.5Cu14.7Ni5.3P22.5 is heated through its SCLR (230290 8C) under an applied pressure of 130 MPa. The process can be well controlled as shown by glassy rods with aspect ratios of 5 (c,d) fabricated by isothermal embossing at 275 8C for 60 s. e) To demonstrate the nanoformability, very-high-aspect-ratio (>200) structures were formed. f) The hot-scrapping method described in Section 3.3.2 can be used to create free-standing nanorods. Reproduced with permission from [280]. Copyright 2009, Nature Publishing Group.

3.3.5 Extrusion The thermoplastic formability of BMG formers can also be made use of for extrusion. Extrusion produces the highest-aspect-ratio shapes, 100, of constant cross-section. Early work on extrusion of BMGs focused on consolidating BMG powder and processing in the SCLR. Kawamura and co-workers pioneered this method[321,322] and achieved full strength compacts using ZrAlNiCu powders.[323,324] For the same alloy the relationship between extrusion temperature, pressure, and ram speed was determined and summarized in an extrusion map.[325] Based on these ndings and theoretical considerations, the authors concluded extrusion length of up to one meter for a 3-mm diameter may be achieved under practical pressures. Various BMG formers can be used for extrusion, resulting in different extrusion ratios. An extrusion ratio of up to ve was achieved with minimal crystallization for CuTiZrNi.[326] Similar results were obtained for Cu54Ni6Zr22Ti18,[327] Cu50Ti32Zr12Ni5Si1,[328] and Zr58.5Nb2.8Cu15.6Ni12.8Al10.3.[329] Extrusion was also used as a consolidation and synthesis method for BMG composites through partial crystallization[322,330] or

through mixing amorphous with crystalline particles.[331,332] Research has also been focused on exploring extrusion as a process to fabricate constant cross-sectional BMG proles.[325,333] Figure 15 depicts a 2-mm diameter Zr44Ti11Cu10Ni10Be25 wire exceeding 50 cm in length, which was extruded under a ram pressure of 400 MPa.[333] Within the same publication a theoretical description was developed based on Hagen Poiseuille Equation (1) when considering entry and exit effects.[333] During the extrusion process, after exiting the effective die length, the material swells signicantly.[325] Kawamura et al.[325] explained this swelling with the Barus effect, an elastic recovery typically observed during stress relaxation in polymers.[334,335] However, other research[333] excluded that the Barus effect is responsible for the swelling of BMG formers during exiting the extrusion die. It was argued that the elastic deformation of BMGs at the TPF-processing temperature are much too small to explain the observed die swelling with viscoelastic effects.[333] For example, for Zr44Ti11Cu10Ni10Be25 at the extrusion temperature of 463 8C, the ow stress for a strain rate d 0.1 s1 is 3 MPa.[120] With a modulus of 97 GPa, the elastic strain equals 3 105, which is negligible compared to the observed swelling of approximately 1.5 101. Therefore, Chiu et al.[333] concluded as an explanation for the swelling that an increase of the extrudate diameter occurs in low-Reynolds-number ows of Newtonian uid, owing to the sudden change of the boundary conditions at the die end.[333] Inside the die conduit, the material satises the non-slip boundary conditions on the die walls with a steady-state parabolic velocity prole requiring a perpendicular velocity component. Outside the die, there is no viscous traction at the free surface of the extrudate, thus the parabolic ow changes into the plug ow characterized by a constant velocity prole. Owing to the incompressibility condition, this change requires a non-zero radial ow component, which causes the swelling. Numerical studies of the extrudate-swell problem[336,337] have established that a creeping Newtonian jet emerging from a long cylindrical die expands, independent of the conduit diameter, by about 13%. This value is similar to the swelling of 1417% that has been observed for Zr44Ti11Cu10Ni10Be25.[333]

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TPF-based extrusion of BMG formers offers a valid fabrication method for constant cross-sectional diameter proles. BMG former with high formability should be chosen for TPF-based extrusion, since the required forming pressure scales directly with the BMG formability. The dimensional accuracy of this process is, however, limited due to the unavoidable but predictable swelling. 3.3.6. Rolling

Metals are most commonly obtained in the form of sheets. Sheets are either used directly as an end product or are processed further using one of the many sheet-forming technologies.[338] About 90% of sheet metal is produced by rolling. Rolling for metallic glasses can be categorized into two processes, which are schematically shown in Figure 16A. One is based on liquid processing and the other on thermoplastic forming. Melt spinning is one of the earliest examples of liquidprocessing-based rolling.[340,341] Within melt spinning, the liquid sample is quenched by injecting on a single, fast-spinning copper roll. To improve the control over sheet dimensions, in particular the thickness, twin-roll casting has been employed. Simulations suggest that twin-roll casting can be extended into a continues process.[342] Research focused on controlling thickness and surface roughness of the rolled sheets.[343] Recently, sheets have been produced from Fe-based BMGs[344,345] under adequate control over sheet dimensions processed in a continuous way.[344] During liquid-phase rolling even the highest practical strain rates result in homogeneous deformation (see Fig. 16B). On the other extreme is cold rolling, where the amorphous BMG is rolled at room temperature. Due to shear localization in this deformation region (see Fig. 16B), cold rolling is limited to already initially thin, <1 mm, samples to prevent catastrophic failure along a dominant shear band. In addition, the strain per pass is very limited and consequently a large number of passes are required to achieve signicant overall strains. It has been found, however, that cold rolling affects the mechanical properties of BMGs. For Zr55Cu30Al10Ni5, plasticity, even in tension, increases with cold rolling through the introduction of shear bands.[346,347] Similar observations were made Figure 16. A) Schematic images of rolling processes used for BMGs. Left: Liquid-based twin when cold rolling Zr41Ti14Cu12Ni10Be23 rolling, in which the BMG-forming alloy at a temperature above its liquidus temperature is BMG.[348] Cold rolling of elemental lms is brought into contact with the roll. The rolls act as a forming and cooling device. Right: Rolling also a method to create amorphous material based on TPF, in which the rolls typically act solely as a forming device. B) Deformation map showing the dominant deformation mode (shear localization, homogenous Newtonian, and through a solid state reaction.[349354] non-Newtonian ow) as a function of strain rate and temperature. The open symbols are data for Comparable thermal stability to rapidly Zr41Ti14Cu12Ni10Be23 [339] and the solid symbols are data for Zr44Ti11Cu10Ni10Be25 (shear quenched material was achieved through localized (~) and homogeneously deformed (&)). The two sets of data follow a similar trend this process indicating a homogeneous mix- and indicate that homogeneous deformation can be extended to high strain rates for sufciently ture of the constituents of the alloy.[350] high temperatures. C) Final diameter of Zr44Ti11Cu10Ni10Be25 discs after pack rolling at various Therefore, cold rolling is a useful tool to temperatures. The strain increases continuously and reaches a maximum at 500 8C. For higher processing temperatures (partial) crystallization reduces overall strain. The starting discs were alternatively create amorphous metals and 11 mm in diameter and 3 mm in height. D) Large thin sections can be created by TPF-based alternate its mechanical properties. As a sheet hot-rolling with high surface nish. E) Demonstration of the ability to replicate microfeatures as production method, however, it is of limited small as 300 nm during pack rolling. Reproduced with permission from [285]. Copyright 2008, use. Elsevier.

Making use of the homogeneous deformation behavior in the SCLR and the large formability of a wide range of BMG formers, rolling has been carried out at different temperatures in the SCLR.[285,355357] Various forms of starting material were used including powder.[357] Using Zr44Ti11Cu10Ni10Be25, the deformation mode and the achievable strains as a function of temperature during TPF-based rolling have been explored, using a pack rolling approach to establish a stable processing temperature.[285] This approach enabled large homogeneous strains as high as 1400%, which are induced by strain rates of up to 70 s1, which have been achieved by single-pass hot rolling of Zr44Ti11Cu10Ni10Be25 in its supercooled liquid state (Fig. 16CE). Homogenous deformation could be achieved over a temperature range of 120 8C (Fig. 16B). When the rolling was combined with microreplication, features as small as 300 nm could be precisely replicated within the hot-rolling process (Fig. 16E).[285] These advances are important for TPF-based hot rolling to be developed into a fabrication method for high-quality BMG sheets. Developing a commercially viable process based on the above proof of concept must involve a precise control over the processing temperature.

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3.3.7. Blow Molding Although TPF-based hot rolling and extrusion provides methods to achieve high aspect ratios, the geometric range that can be achieved with these techniques is limited to rolling into planar shapes and to extrusion to a constant cross-section. Net-shaping of complex 3D shapes, which are large compare to their wall thickness, using TPF-based techniques such as compression molding is challenging due to the friction between the mold and BMG, which often requires impractically high pressures. For example, to deform a Zr44Ti11Cu10Ni10Be25 rod of 10 mm diameter and 30 mm height into a disc of 60 mm diameter and 0.8 mm height a forming pressure of 30 MPa is required, about 100 times higher than the ow stress of the alloy at this temperature and strain rate.[286] Friction between the forming BMG and the mold can be reduced to some degree by using lubricants, which result in some slippage. The improvement is quite limited and the use of lubricants also sacrices the otherwise excellent achievable surface nish. A more effective strategy to reduce forming pressure is to reduce the contact area between BMG and mold. This is the case for the previously discussed hot-rolling (see Section 3.3.6) where the contact area reduces to a 2D-line contact. A similar effect is observed in an extrusion process where the contact area is reduced to the effective die length (see Section 3.3.5). Friction can be eliminated altogether during free expansion in blow molding. Even when blow molding into a mold, the vast majority of lateral straining is achieved before the deforming BMG comes into contact with the mold. From a practical point of view, a pressure difference of 1 atm (105 Pa) is desired for blow molding of BMGs. This pressure difference can be accomplished by creating a (low) vacuum on one side. We estimate the maximum strain that can be achieved with a Zr44Ti11Cu10Ni10Be25 BMG former, when blow molding under such a pressure difference of Dp 105 Pa, for a membrane of radius r 20 mm and thickness t 1 mm.[286] The stresses acting in the walls of a diaphragm can be estimated by the stresses in a hemisphere:

limited by tonset. This results in a maximum strain that can be achieved. (Eq. (12))

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"max

sH tonset 3h

(12)

To calculate the maximum stress and maximum strain as a function of temperature according to Equation (11) and (12) (Fig. 17) viscosity and crystallization time data for Zr44Ti11Cu10Ni10Be25[120] were used. From these calculations, it is clear that the maximum strain increases continuously with increasing forming temperature from 15% at 370 8C and "max 2 105 s1 to 32200% at 500 8C and "max 11 s1. The increase in maximum strain rate with increasing temperature stems from the fact that the temperature dependence of the viscosity, as shown in Figure 7A, is larger than the temperature dependence of the crystallization time (see Section 3.2). Figure 17 suggest a wide processing window for blow molding of BMG former, where very large deformations can be achieved before crystallization sets in. Such a commercially viable processe requires an available process time between 100 s and 1000 s and strain rates between 102 s1 and 1 s1. The above calculations suggest that with Zr44Ti11Cu10Ni10Be25 such requirements would be fullled in a temperature window from 430 8C to 480 8C, where strains between $400% and $13000% are achievable.[286] Figure 18 shows some examples of blow molding with Zr44Ti11Cu10Ni10Be25, for which strains of up to 400% were achieved. When exceeding this value, the deforming BMG hemisphere bursts, as shown in Figure 18B, despite the suggestions of Equation (12) of strains exceeding 5000% at this temperature. This limitation is due to thinning, which is referred to as the non-uniform decrease in wall thickness during expansion (see, e.g., ref. [358]).

s H Dp

r 2t

(10)

Under these conditions sH 1 MPa, which acts in the shell of the hemisphere. For the BMG to undergo plastic deformation, its ow stress has to be lower than sH, which requires _ s flow h 3" < s H . As an example, this requirement is fullled for Zr44Ti11Cu10Ni10Be25 at a temperature of 460 8C and a strain rate of 101 s1 and can be calculated from h (460 8C) 3.1 106 Pa _ s[120] using s flow h 3" and assuming Newtonian behavior to sow 0.94 MPa. These ndings laid the basis for quantifying the strain that can be achieved under the above conditions. The maximum strain rate is limited to

sH _ " 3h

(11)

Due to the metastable nature of the BMG in its SCLR, the time over which the BMG can be strained with the maximum rate is

Figure 17. Maximum strain and strain rate calculated according to Equation (11) and Equation (12), respectively, for a Zr44Ti11Cu10Ni10Be25 disk of 1-mm thickness and 40-mm diameter under a pressure difference of 105 Pa. Strains between 400% and 13000% are achievable in a temperature window from 430 to 480 8C, where the crystallization times, which are limiting the process, are 440 and 85 s, respectively, suggesting a commercially viable fabrication process. Reproduced with permission from [286]. Copyright 2007, Elsevier.

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Thinning can have two origins: One is geometrical, where for most geometries the hydrostatic gas pressure during blowmolding results in a non-uniform stress distribution within the deforming BMG. This stress distribution results in non-uniform straining and, consequently, in a non-uniform decrease in thickness throughout the expanding BMG. The other origin for thinning is the strain-rate dependent ow resistance of the material, which is reected in the strain-rate-sensitivity ds _ exponent, m dflow . Extrapolations of s flow "data for _ " Zr44Ti11Cu10Ni10Be25, at temperatures where blow molding is typically carried out,[339] suggest m 1. Under these conditions the faster deforming areas experience the largest resistance possible (at least for metals), which decreases the strain rate and acts as a stabilizing effect. As a comparison to BMGs, the strain-rate-sensitivity exponent for superplastic-deformable titanium alloys is between 0.30.7, where specic measurements are dependent on the material, the strain rate, the temperature at which deformation takes place, and the stability of the microstructure.[358,359] As a result, thinning in BMGs during blow molding is signicantly reduced compared to the thinning in super plastic formable Ti- and Al-alloys.[360] Finite element modeling has been used to determine the plastic deformation of BMG former during TPF-based processes.[291,361364] We used it to model the thinning of a 20-mm-radius and 1-mm-thick Zr44Ti11Cu10Ni10Be25 disk deformed under DP 105 Pa. Newtonian behavior was assumed with h 3.1 106 Pa. The predictions of the model coincide with the latitude where bursting is experimentally observed (Fig. 18B).

Figure 18. A) Strains of up to 400% can be achieved when blow molding a disc of 40-mm diameter and 1-mm thickness Zr44Ti11Cu10Ni10Be25 under a pressure difference of 105 Pa. Reproduced with permission from [286]. Copyright 2007, Elsevier. B) For larger strains, >$400%, the blow-molded sample burst due to thinning. C) Finite element modeling, considering Newtonian ow, conrms the latitude where the expanding BMG is thinnest and, thereby, most likely to burst. D) The effect of pre-shaping (to reduce thinning) on the maximum strain rate that can be evaluated when blow molding Zr44Ti11Cu10Ni10Be25 into a cylindrical mold [291].

Furthermore, predictions of our model are in good agreement with nite element modeling predictions, which use a more complex constitutive equation, where also the phenomena of stress overshoot is considered.[363] The results, shown in Figure 18, conrm the experimentally observed thickness distribution and thereby the assumption of Newtonian behavior. Geometrical thinning can be reduced by preshaping the BMG feedstock for a desired nal shape. For example, disks that are non-uniform in thickness can be used to increase the overall strain. This approach is shown in Figure 18D, where the preshaped disk is designed thicker in the center, where it undergoes the largest strain. The overall strain for a preshaped disk lled into a cylindrical mold increases from 470% for tmax/ tmin 1 to 680% for tmax/tmin 3 (tmin, tmax minimum and maximum thickness of disc). Once this ratio is exceeded, the structure becomes instable and premature bursting occurs at a different locations, as observed and predicted by nite element modeling. The use of disc-shaped preshapes that are non-uniform in thickness increase the achievable overall strain. However, the achieved strains are still signicantly lower than the calculated maximum strain proposed by the formability of the material (Fig. 17). To blow mold more complex geometries and use the ability to undergo strains >1000%, further preshaping is required. Inspired by techniques used in plastic blow molding, where parisons are used, we utilized nite element modeling to determine the shape of a parison for complex nal geometries (Fig. 19).[291] Snapshots of the modeled expansion during blow molding of a hollow nger-shaped parison with a wall thickness of 2 mm and an inner diameter of 11 mm are shown in Figure 19. The model suggest that this parison geometry results in an acceptable thickness uniformity of the nal part, which was experimentally conrmed.[291] In particular when preshaped parisons are used, BMGs can be blow molded into shapes that were previously not achievable with any metal processing method. Examples of such shapes are given in Figure 20. They include hollow seamless shapes, which can comprise of complex undercuts, and very large thin sections. Due to the low forming pressure, together with the ability to replicate smallest features, as shown in Figure 20D, the dimensional accuracy that can be achieved with this process is even superior over other TPF-based processes. In addition, this method is capable to combine the three processing steps typically required for metal processingshaping, joining, and nishinginto one step.[365] For example potential joints such as threads, as shown in Figure 20EH can be formed in the BMG during the expansion process. Surface nishes that can be achieved with blow molding of BMGs include mirror nishes (Fig. 18A) as well as a wide range of other patterns (Fig. 20D). The low forming pressure and temperature required for blow molding of BMGs suggest a comparison to the blow molding of plastics. One apparent difference is the limited formability of BMGs due to the eventual onset of crystallization of BMG formers as discussed above. However, this difference does not impose a practical limitation because the strains that can be achieved with blow molding of BMGs can exceed 10000% (Fig. 17), sufcient for the vast majority of shapes. There are, however, differences in some properties of BMGs and plastics that are relevant for blow molding. Most notable is the sensitivity

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Figure 19. Top: Finite element modeling is used to determine the required shape of the parison to blow mold Zr44Ti11Cu10Ni10Be25 into a rectangular-shaped mold. Bottom: Expansion of a Zr44Ti11Cu10Ni10Be25 parison with 2-mm wall thickness under a pressure difference of 105 Pa for 60 s results in complete lling of the mold [291].

of the ow stress to temperature. This is reected in the steepness index, m d logh=6 ,[366] where values of BMG formers dTg =T ranging from m 69.6 for Ni60Nb35Sn5[104] to m 38.3 for Zr41Ti14Cu12Ni10Be23[122] have been reported. A large steepness index corresponds to a fragile-liquid behavior, while a smaller value corresponds to a strong liquid with nearly Arrhenius behavior (see Fig. 1). Within this classication scheme BMGs can
TTg

be considered moderately strong liquids.[84,87,104] Polymers used for blow molding, on the other hand, can be considered very fragile.[366] For example, a steepness index for poly(vinyl chloride) (PVC) and polypropylene (PP) of 191 and 137, respectively, was reported.[367] The fact that the ow stresses in polymers are signicantly more sensitive to temperature than they are in BMG formers suggests a larger effect of temperature gradients within the blow-mold setup on the deformation kinetic of polymers than

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Figure 20. Blow molding with BMGs permits hollow, thin, seamless shapes, which can include undercuts. These shapes were previously unachievable with any other metal processing method (AC). The surface can be patterned, e.g., to reveal a hologram (D), joints can be created such as threads (F,H), and a second material can be joined to the BMG (E) in the same processing step than the blow molding [291].

on BMGs. This attribute suggests a blow-molding processing advantage of BMGs over polymers because a given temperature gradient in the blow-molding material has a larger effect on the deformation behavior on polymers than on BMGs. However, controlling temperature and unwanted temperature gradients within the deforming material is more challenging for BMGs than for polymers. This challenge is due to the different thermal conductivity of BMGs and polymers. For BMGs, the thermal conductivity is approximately 10 W m1 K1.[368,369] This value is almost two orders of magnitude higher than the thermal conductivity for polymers used for blow molding such as PVC, PP, polyethylene (PE), or poly(ethylene terephthalate) PET.[370] As a consequence, any unwanted temperature gradient within the blow-mold setup is adopted much faster in the BMG than in plastic. Thereby, a given (unwanted) temperature gradient within the blow-mold setup translates signicantly faster into a temperature gradient in the BMG, which likely overshadows the otherwise processing advantage of BMGs due to their relative temperature insensitivity of the ow stress. The most severe consequence of this effect is present in thin sections, where convective cooling is most effective due to the large ratio of surface area to thermal mass. Further research is required to develop processes within temperature gradients can be reduced

to result in an overall blow-molding processing advantage of BMGs over polymers. Blow molding in a liquid medium, which provides higher temperature uniformity, is one promising strategy.[291] Altogether, blow molding of BMGs is the most versatile process strategy for complex and precise 3D articles. In an experimental setup where unwanted temperature gradients can be reduced BMG former are as (or even better) suitable for blow molding than currently used thermoplastics. Within such a setup, geometries can be net-shaped in an economic and environmental benign process that was previously unachievable with any metal processing method. The excellent surface nish of blow-molded BMG samples and the ability to precisely pattern the surface and to mechanically lock a second phase can be used to combine shaping, joining, and nishing into one processing step. 3.3.8. Amorphous Metallic Foams The unique processing opportunity in BMG formers was also explored for the synthesis of amorphous metallic foam. Metallic foams are becoming increasingly attractive as structural materials. Their attraction is to a large extent due to their high stiffness in conjunction with very low specic weight and high energy-absorption capability.[371] Foams can be classied as either

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open or closed pores. Open foams are characterized by interconnected bubbles and are mainly used as functional materials. Closed foams are characterized by spatially separated bubbles and are attractive as structural materials. Because foam is an unstable structure, the process of foaming of pure metals is a challenging task. The dynamics of bubble nucleation, growth, sedimentation, impingement, and collapse scale inversely with viscosity. The viscosity of a pure metallic liquid at its melting temperature is of the order of 103 Pa s.[87] The viscosity of a BMG former at its liquidus temperature is of the order of 1 Pa s.[314] Therefore, the foaming kinetics of BMGs can be expected to be drastically reduced compared to pure metals. To establish foaming kinetics in pure aluminum comparable to what can be expected in BMG formers, experiments were even performed in space under microgravity conditions.[372] The sluggish kinetics of BMG-forming liquids suggests better control over bubble-size distribution, spatial homogeneity, and bubblevolume fraction in a foam synthesis process. The rst amorphous metallic foam was produced by expansion in the liquid phase of water vapor bubbles generated from hydrated boron oxide ux powders followed by quenching.[373] During this liquid processing, the $20 mm bubbles that are contained in the liquid Pd43Ni10Cu27P20 are expanded by rapidly reducing the processing pressure. Simultaneously, the bubbly liquid was quenched to avoid crystallization during solidication. This results in close-cell foam with porosities of up to 85 vol.% and pore sizes ranging from 2001000 mm (Fig. 21A). Based on the same method, PdNiCuP can be foamed by expansion of hydrogen bubbles precipitated from a supersaturated melt, yielding porosities of up to 65%, with pore sizes around 80 mm (Fig. 21c).[374376] Similarly, ZrH2, a commonly used gas releasing agent, can be used to foam Fe48Cr15Mo14Y2C15B6.[377] An alternative approach to the expansion of gas bubbles are beds of NaCl particles. After quenching, the particles can be removed in an additional dissolution step.[378] This idea of using spaceholders was extended to different alloys/spaceholder combinations such as the commercial Zr57Nb5Cu15.4Ni12.6Al10 (Vit106) BMG-forming alloy, which was produced by melt inltration of beds of hollow carbon microspheres with diameters of 2550 mm.[379] In addition, BaF2 can be used, which was inltrated by Zr57Nb5Cu15.4Ni12.6Al10,[380] resulting in uniform open-cell foam with a porosity of up to 85% distributed in pores of about 200-mm size (Fig. 21B). An open-cell structure with a fully interconnected porosity of 65 vol.% of 125250 mm in Pd42.5Cu30Ni7.5P20 has also been reported.[380] Furthermore, a similar foam with lower porosity of approximately 40%, distributed in pores of 5001000-mm size was fabricated from Zr41.25Ti13.75Cu12.5Ni10Be22.5 using NaCl space holders.[381] In addition, hollow iron spheres where inltrated using a Mg60Cu21Ag7Gd12 BMG-forming alloy.[382] To create a porous BMG structure, a phase decomposition process, which occurs during solidication of Y20Ti36Al24Co20, can be employed.[182] In a subsequent etching step one of the phases can be preferentially etched, leaving an open-cell porous structure.[383] Due to the length scale of the decomposition process the pore size of 15150 nm in the structure is the nest reported to date, as shown in Figure 21E. All the above described synthesis techniques are based on liquid processing, where the foamed BMG former (BMG

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Figure 21. Amorphous metallic foam (AMF) synthesized through different methods. A) Pd43Cu27Ni10P20 AMF with $80% porosity, synthesized by liquid expansion of gas pores that are created by processing the BMG in B2O3. B) Zr-based AMF of $80% porosity made by liquid inltration of BaF2 salt particles followed by removal of those particles in an acid bath. C) Liquid expansion of hydrogen pores in Pd42.5Cu30Ni7.5P20 resulting in AMF of up to 64% porosity. D) Melt inltration of La2O3 compact with ZrNbAlNiCu resulting in open-cell AMF. E) Selective dissolution of one phase from a two-phase Ti-based metallic glass resulting in the nest open-cell structure. F) Ni59Zr20Ti16Si2Sn3 AMF synthesized through warm extrusion of a mixture of BMG powder and brass, which is subsequently dissolved. The volume fraction of porosity is $40%. G) Pd43Cu27Ni10P20 AMF synthesized through TPF expansion of pressurized B2O3 inclusions. H) Overall expansion of the AMF shown in (G) results in a porosity of up to 85%. Panels (AH) are reproduced with permission from [373], [384], [374], [385], [383], [386], and [387] (G,H), respectively. Copyright, respectively: 2003, American Institute of Physics; 2005, Elsevier; 2004, Japan Institute of Metals; 2007, Japan Institute of Metals; 2006, Elsevier; 2006, American Institute of Physics; 2004, American Institute of Physics (G,H).

spaceholder) must be cooled faster than the critical cooling rate to avoid crystallization during solidication. This imposes several limitations: the most general is the limitation of their size to the maximum casting thickness. In particular, for the use of amorphous metallic foams in structural applications the size limitation prevents the materials from a wide range of applications. An additional drawback of the liquid processing

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method is the limited control and ability to vary the porosity in the foamed structure. In an attempt to overcome these limitations, foam-synthesis methods were developed that are based on thermoplastic forming (Fig. 22A). Within this process, the required fast cooling and expansion into foam are decoupled. In a rst processing step, a gas or gas-releasing agent is distributed into small bubbles in the liquid BMG at a temperature above Tl. A small individual size of the bubbles limits their sedimentation velocity according to vsed $ dbubble2. In a second step, the mixture of BMG and gas (or releasing agent) must be cooled faster than the critical cooling rate of the alloy. In the nal step, the BMGgas mixture is reheated into the SCLR under a processing pressure that is lower than the pressure during step 1 and 2. This pressure difference causes the encapsulated gas to expand, whereby the size of the amorphous metallic foam (AMF) can be far exceeding the critical casting thickness. When small bubbles created from hydrated B2O3 captured in PdNiCuP during quenching into its amorphous state were thermoplastically expanded, a porosity of up to 85% was achieved.[387] This porosity could be precisely controlled. Based on the same idea Zr48Cu36Al8Ag8 powder is melted under 12 MPa pressurized helium atmosphere, followed by water quenching. The introduced spherical helium pores, with a diameter of 30 mm and an overall volume fraction of 7% are thermoplastically expanded to result in a close-cell foam of overall volume fraction up to 70%.[388] For a variety of BMG formers thermoplastical expansion has been precisely controlled resulting in a close-cell foam of overall volume fraction up to 85% (Fig. 21g,h).[284,387392] Within this TPF-based foam-synthesize method, the size limitations exposed by the critical casting thickness is lifted[387] due to the fact that the dimensions are only limited to the critical casting thickness in step 2 (Fig. 22B) to render its amorphous state. Subsequent expansion into a foam with overall dimensions that can signicantly exceed the critical casting thickness in step 3 and cooling to ambient temperature does not cause crystallization as long as the processing time is limited to below the crystallization time. After TPF-based expansion, fast cooling is no longer required. Therefore, this multi-step-AMF synthesis method based on TPF expansion is technologically more promising when targeting structural applications rather than liquid-

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Figure 22. A) Schematic image of the TPF-based foam-synthesis method. A gas or gas-releasing agent is distributed in the liquid BMG at a temperature above Tl. In a second step, the mixture of BMG and gas (or releasing agent) is cooled faster than the alloys critical cooling rate. In the nal step, the BMGgas mixture is reheated into the SCLR under a processing pressure that is lower than the pressure during step one and two. The pressure difference causes the encapsulated gas to expand. Final dimension of the foam can exceed the critical casting thickness because the required fast cooling and forming are decoupled. B) Schematic overview of the effect of porosity on the mechanical properties in porous and amorphous metallic foam. For a small porous volume fraction, shear band disruption results in an increase in plasticity. Shear band stabilization occurs when ligament dimensions decrease below approximately 10 times the plastic zone in the BMG former. For highest volume fractions, >95%, ligaments within the foamed structure buckle elastically, resulting in signicant global elasticity. The absolute values of critical porosity depend on specic properties of the BMG former, the one schematically depicted here is approximated for a medium range Zr-based BMG former.

processing-based amorphous foam-synthesis methods. The potential of this approach is reected in the recent shift of foam-synthesis methods using this TPF-based process.[284,387392] Warm extrusion methods of BMG powder and a mixture of various second phases are based on the TPF processing rather

Table 6. Summary of amorphous metallic foams, their synthesis method, chemistry, and characteristics.
Method Foam Structure Closed Closed Closed Closed Open Open Closed Open Closed Closed Porosity [%] <85 <70 <60 3585 $65 $60 85 3040 70 70 Pore Size [mm] 2001000 $200 2550 351000 120250 50 501000 0.150 30200 100 Size Limitation <dc <dc <dc <dc <dc <dc No No No No Alloys Pore Creating Media B2O3 H2 Hollow carbon, hollow iron BaF2, NaCl NaCl La2O3 B2O3 Selective dissolution: Cu bronze Helium pores Helium pores Comment Reference

Liquid state

PdNiCuP PdNiCuP, ZrNbCuNiAl MgCuAgGd ZrNbCuNiAl ZrTiCuNiBe PdNiCuP PdNiCuP CuTiZrNiSi NiZrTiSiSn Zr48Cu36Al8Ag8 Zr48Cu36Al8Ag8

First AMF made

[373] [374376,397] [379,382] [380,398] [378] [385] [284,387] [389,390] [386,393] [388,399] [388]

TPF

As a bone replacement material First TPF-based AMF synthesis method

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www.advmat.de www.MaterialsViews.com Table 7. Process-selection map for generic shapes that can be fabricated with various TPF-based BMG fabrication methods.
Process Process Shape Based on Size Shape/ Aspect Ratio 110 Shape Feature Process Level of Maturity R&D medium BMG Former Used Surface Finish Dimensional Issues/Comment Accuracy

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Compression molding; Injection molding Blow molding

TPF

Millimeters to centimeters

Undercuts open

Zr44Ti11Cu10Ni10Be25 [81,82] Pd40Ni10Cu30P20 [117] Zr35Ti30Be27.5Cu7.5 [292] Zr44Ti11Cu10Ni10Be25 [286] Pt57.5Cu14.7Ni5.3P22.5 [291] Au49Ag5.5Pd2.3Cu26.9Si16.3 [291] Zr35Ti30Be27.5Cu7.5 [291] Zr53Ti5Cu20Ni10Al12 [240] Zr65Al10Ni10Cu15 [364] Zr44Ti11Cu10Ni10Be25 [285]

Very good

Good

Mold release; Mold wear due to high required forming pressures can be combined with surface patterning <1 mm. Most versatile shapes possible. Can be combined with joining and surface patterning <10 mm. Size is limited by the maximum casting thickness of pre-shape only. Temperature-control critical; Aspect ratio and shape size can be increased to 1 in a continuous process Swelling $15% has to be considered; Sharp corners round off

TPF

10 mm to centimeters (10)

101000 Hollow, R&D high undercuts; Low symmetry

Excellent

Excellent

Hot-rolling

TPF

Millimeters to centimeters (10)

100

Sheets

R&D low

Good

Moderately good

Extrusion

TPF

Millimeters to meters

100

Long xed crosssectional prole, hollow

R&D low

CuTiZrNi [326,327,329] Mg85Y10Cu5 [410] Zr41.2Ti13.8Cu12.5Ni10Be22.5 [411]

Good

Moderate

Microimprinting TPF (miniature imprinting, hot-embossing)

Micrometers to millimeters

110

Surface patterning

Zr65Al10Ni10Cu15 [323] Ti50Cu18Ni22Al4Sn6 [412] Mg58Cu31Y6 [413] Zr44Ti11Cu10Ni10Be25 [333] R&D Industrialization La55Al25Ni20 [414] Pt48.75Pd9.75Cu19.5P22 [298,415] Zr-Al-Cu-Ni [296,416,417] Zr44Ti11Cu10Ni10Be25 [245,418,419] Pt57.5Cu14.7Ni5.3P22.5 [245] MgCuY [313] Au49Ag5.5Pd2.3Cu26.9Si16.3 [245] Zr41.2Ti13.8Cu12.5Ni10Be22.5 [302] Zr46.8Ti8.2Cu7.5Ni10Be27.5 [420] Pd40Ni40P20 [303,418] Ce68Al10Cu20Nb2 [50] Pd76Cu7Si17 [289,421] Zr44Ti11Cu10Ni10Be25[245] Pt57.5Cu14.7Ni5.3P22.5 [245,295,422] Au49Ag5.5Pd2.3Cu26.9Si16.3 [245] Pt57.5Cu14.7Ni5.3P22.5 [245] Au49Ag5.5Pd2.3Cu26.9Si16.3 [245] Zr44Ti11Cu10Ni10Be25 [245]

Very good

Good

Typically disposable molds; Can also be combined with compression molding, hot-rolling, injection molding, and blow molding

Miniature manipulation

TPF

Nanometers to millimeters

$1

R&D low

Bending, scrapping, smoothening

Miniature fabrication

TPF

Micrometers to millimeters

110

3D parts; R&D high No undercuts; Design freedom in 2D, other dimension perpendicular Rods R&D medium

Very good Good to excellent

Combines microimprinting, scrapping and/or manipulation, and surface smoothening

Nanoimprinting TPF

<100 nm

1100

Die-casting

Direct casting Direct casting

Millimeters to 10 centimeter Millimeter to 10 centimeter

1100

Undercuts

Commercially used R&D high

ZrAlCuNi [290] Pt57.5Cu14.7Ni5.3P22.5 [280] Au49Ag5.5Pd2.3Cu26.9Si16.3 [280] ZrAlCuNi [235] Zr41.2Ti13.8Cu12.5Ni10Be22.5 [82] Zr57Nb5Cu15.4Ni12.6Al10 [82]

Very good

Good

Relies on BMG-mold material combinations Internal stresses, casting defects, porosity; Sliders needed for undercuts Signicant reduction of casting defects over die-cast articles; Sliders needed for undercuts

Moderate

Moderately good Good

Counter gravity casting

1100

Undercuts

Good

than TPF expansion. They can also be used to create porous and foamed amorphous metals.[386,393396] A summary of amorphous metallic foams, their synthesis method, chemistry, and characteristics is given in Table 6. Introducing porosity into amorphous metals can have signicant effects on their mechanical properties. The mechanisms that control the mechanical properties are summarized in Figure 22B. When small volume fraction of porosity, <4%, are

used, a compressive plasticity of up to 25% is observed, compared to $0% for the same BMG in bulk form.[164] The improvement in plasticity can be explained by the pores hindering the propagation of shear bands. This mechanism is similar to the ductilization of metallic glasses by a second phase in BMG composites.[58,400407] The required volume fraction of pores to disrupt shear bands is given by the condition that shear bands have to intersect with a pore on the length-scale shorter or equal to the processing zone of

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the corresponding BMG. This volume fraction varies signicantly due to variations of the processing zone[408] from approximately 10 mm for brittle BMG formers[7476] up to over 1 mm for the toughest BMGs.[62] For a medium-range Zr-based BMG, this volume fraction can be estimated to be approximately 5%. When the porosity approaches values that the corresponding ligament dimension, the interporous spacing, approaches about 10 times the critical crack length, shear band stabilization sets in. As a result, the corresponding porosity for a medium-range Zr-based BMG former is above 60%. This size effect, which results in bending ductility, was originally explained for BMG beams as a result of a decreased shear offset in a shear band with decreasing beam thickness.[72,73] An increase in compressive strain to failure due to this effect was observed for a wide range of porous and foamed amorphous metals.[376,384,398] With increasing porosity a transition from plastic collapse to elastic buckling can be expected when approaching high porosity. The critical porosity, which can be estimated by the ratio l/t, where l is the length of the ligament (pore diameter) and t its thickness (pore spacing) above which the deformation changes from plastic collapse to elastic buckling, is dened by (t/l)crit $ 3(sy /E)bulk (sy: yield strength, E: Youngs modulus) (see, e.g., ref. [408]). Metallic glasses have a much higher sy /E ratio of about 5 102 than, e.g., aluminum with 3 103. This difference results in a critical porosity in AMF of approximately 95% for elastic buckling compared to an impractical 99.7% in Al foams. Experimental evidence of this effect was provided recently in Pd-based BMGs where elastic buckling of some of the ligaments was observed.[392,409] AMFs are promising structural materials due to their superior mechanical properties. In particular, for high porosity, >$60%, their mechanical properties stem from the geometrical effect provided by the foams architecture, which provides signicant plasticity in addition to the attractive properties of the (bulk) BMG. Due to the lift of geometrical constrains to the critical casting thickness, but equally important, precise control over porous distribution and volume fraction, AMF synthesis methods based on thermoplastic expansion are most promising for the fabrication of larger parts, typically used in structural applications. Liquid processing limits the AMF to below its critical casting thickness but might be useful for synthesizing functional foams (or porous media). Such functional foams will be relevant especially for lter or catalyst applications.

scale over which BMGs can be precisely net-shaped spans over 7 orders of magnitude, from $10 nm to 10 cm. Geometries that were previously unachievable with any metal process are possible with TPF-based processes. The low processing temperature and forming pressure, particularly for blow molding, together with the ability to combine shaping, joining, and nishing into one processing step yields an economical, energy efcient, and green fabrication method. Continuation of the rapid proliferation of BMG technology hinges on material costs and the advancement of TPF-based processing methods for commercial adaptation. Specic research should be targeted toward the development of inexpensive BMG formers with high formability. Furthermore, commercial adaptation of TPF-based processes requires research that addresses scale-up, cycle time, as well as reuse and recycling of BMGs. The mechanical properties of BMGs, which have occasionally been identied as the reason for limited proliferation, do not in fact impose a limitation for a wide range of specic applications. This is particularly the case when proposed applications are targeted to replace plastics. To appreciate their full range of attractive properties as a structural material, BMGs should, however, be used in geometries where at least one dimension is comparable with the processing zone. Resolving these issues might result in a societal impact of BMGs similar in magnitude to that of thermoplastics in the 20th century.

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Acknowledgements
The author would like to thank Bill Johnson, Golden Kumar, Ralf Busch, Andy Waniuk, Quoc (Tran) Pham, Amish Desai, and A. J. Barnes for fruitful discussions and Michelle Adelman for help with organizing the manuscript. Financial support is acknowledged from National Science Foundation (MPM #0826445), (NM# CMMI-092 8227)Yale Nanoscience and Quantum Engineering seed grant, US Army through W15QKN-09-C-0067 Phase II SBIR. Finally, we thank the authors of many of the original articles cited in this review for providing high-resolution images of their art work. Received: August 13, 2009 Published online: December 17, 2009

4. Summary
BMG alloys now come from a wide range of chemical compositions, several with appealing properties. Crystallization studies reveal that TPF-based processing is the most robust and versatile fabrication method for BMG formers. This technique includes processes inspired by fabrication methods used for plastic processing, such as micro- and nanoimprinting (embossing), micromanipulation, blow molding, and others, all of which are summarized in Table 7. For some BMG formers, the optimum processing parameters are comparable to those used in plastic processing, whereas the combination of processing-related properties suggests additional advantages for BMG processing relative to plastics. The length

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