Nanoshaping of glass forming metallic liquids by stretching: evading lithography.

Lithography-free nanomanufacturing by elongation and fracture of glass forming metallic liquid is presented. The viscous metallic liquid confined in a cavity is laterally downsized to nanoscale by stretching. The extent of size-reduction can be controlled by tuning the active volume of liquid and the viscous and capillary stresses. Very high aspect-ratio metal nanostructures can be fabricated without using lithography or expensive molds. A systematic study is performed using glass forming Pt-Cu-Ni-P alloy to understand the effects of viscosity, surface tension, pulling velocity, and cavity size on the evolution of cylindrical liquid column under tension. The results are quantitatively described using a phenomenological model based on lubrication theory and surface tension induced breakup of liquid filaments. A new manufacturing approach based on variable pulling velocity and/or spinning of metallic liquid is proposed for fabrication of complex geometries.

Functionalization of metallic glasses through hierarchical patterning.

Surface engineering over multiple length scales is critical for electronics, photonics, and enabling multifunctionality in synthetic materials. Here, we demonstrate a sequential embossing technique for building multi-tier patterns in metals by controlling the size-dependent thermoplastic forming of metallic glasses. Sub-100 nm to millimeter sized features are sculpted sequentially to allow an exquisite control of surface properties. The process can be integrated with net-shaping to transfer functional patterns on three-dimensional metal parts.

Nanomoulding with amorphous metals.

Nanoimprinting promises low-cost fabrication of micro- and nano-devices by embossing features from a hard mould onto thermoplastic materials, typically polymers with low glass transition temperature. The success and proliferation of such methods critically rely on the manufacturing of robust and durable master moulds. Silicon-based moulds are brittle and have limited longevity. Metal moulds are stronger than semiconductors, but patterning of metals on the nanometre scale is limited by their finite grain size. Amorphous metals (metallic glasses) exhibit superior mechanical properties and are intrinsically free from grain size limitations. Here we demonstrate direct nanopatterning of metallic glasses by hot embossing, generating feature sizes as small as 13 nm. After subsequently crystallizing the as-formed metallic glass mould, we show that another amorphous sample of the same alloy can be formed on the crystallized mould. In addition, metallic glass replicas can also be used as moulds for polymers or other metallic glasses with lower softening temperatures. Using this 'spawning' process, we can massively replicate patterned surfaces through direct moulding without using conventional lithography. We anticipate that our findings will catalyse the development of micro- and nanoscale metallic glass applications that capitalize on the outstanding mechanical properties, microstructural homogeneity and isotropy, and ease of thermoplastic forming exhibited by these materials.

Controllable nanoimprinting of metallic glasses: effect of pressure and interfacial properties.

The quantitative model proposed here for nanoimprinting by thermoplastic compression molding is focused on bulk metallic glasses (BMGs), but it is also applicable to polymers and other thermoplastic materials. In our model the flow and pressure fields are evaluated using the lubrication theory, and the effect of molding pressure, BMG viscosity, and capillary pressure on the spatial distribution of nanoimprinted features is determined. For platinum-based BMG the theory that takes into account capillary pressure but no other surface stresses agrees very well with experimental results. For palladium-based BMG (prone to oxidation) the extended theory includes an additional threshold pressure required to break the oxide layer that forms on the BMG surface. Our analysis provides important insights into flow behavior of BMG supercooled liquids. In particular, a new method for measuring surface tension and viscosity of BMGs and evaluating the strength of the surface oxide layer is demonstrated.

Size-dependent vitrification in metallic glasses.

Reducing the sample size can profoundly impact properties of bulk metallic glasses. Here, we systematically reduce the length scale of Au and Pt-based metallic glasses and study their vitrification behavior and atomic mobility. For this purpose, we exploit fast scanning calorimetry (FSC) allowing to study glassy dynamics in an exceptionally wide range of cooling rates and frequencies. We show that the main α relaxation process remains size independent and bulk-like. In contrast, we observe pronounced size dependent vitrification kinetics in micrometer-sized glasses, which is more evident for the smallest samples and at low cooling rates, resulting in more than 40 K decrease in fictive temperature, Tf, with respect to the bulk. We discuss the deep implications on how this outcome can be used to convey glasses to low energy states.

Surface Morphology, Compressive Behavior, and Energy Absorption of Graded Triply Periodic Minimal Surface 316L Steel Cellular Structures Fabricated by Laser Powder Bed Fusion.

Laser powder bed fusion (LPBF) is an emerging technique for the fabrication of triply periodic minimal surface (TPMS) structures in metals. In this work, different TPMS structures such as Diamond, Gyroid, Primitive, Neovius, and Fisher-Koch S with graded relative densities are fabricated from 316L steel using LPBF. The graded TPMS samples are subjected to sandblasting to improve the surface finish before mechanical testing. Quasi-static compression tests are performed to study the deformation behavior and energy absorption capacity of TPMS structures. The results reveal superior stiffness and energy absorption capabilities for the graded TPMS samples compared to the uniform TPMS structures. The Fisher-Koch S and Primitive samples show higher strength whereas the Fisher-Koch S and Neovius samples exhibit higher elastic modulus. The Neovius type structure shows the highest energy absorption up to 50% strain among all the TPMS structures. The Gibson-Ashby coefficients are calculated for the TPMS structures, and it is found that the C2 values are in the range suggested by Gibson and Ashby while C1 values differ from the proposed range.

High-throughput drawing and testing of metallic glass nanostructures.

Thermoplastic embossing of metallic glasses promises direct imprinting of metal nanostructures using templates. However, embossing high-aspect-ratio nanostructures faces unworkable flow resistance due to friction and non-wetting conditions at the template interface. Herein, we show that these inherent challenges of embossing can be reversed by thermoplastic drawing using templates. The flow resistance not only remains independent of wetting but also decreases with increasing feature aspect-ratio. Arrays of assembled nanotips, nanowires, and nanotubes with aspect-ratios exceeding 1000 can be produced through controlled elongation and fracture of metallic glass structures. In contrast to embossing, the drawing approach generates two sets of nanostructures upon final fracture; one set remains anchored to the metallic glass substrate while the second set is assembled on the template. This method can be readily adapted for high-throughput fabrication and testing of nanoscale tensile specimens, enabling rapid screening of size-effects in mechanical behavior.

Shape-Controlled Metal-Metal and Metal-Polymer Janus Structures by Thermoplastic Embossing.

We report the fabrication of metal-metal and metal-polymer Janus structures by embossing of thermoplastic metallic glasses and polymers. Hybrid structures with controllable shapes and interfaces are synthesized by template-assisted embossing. Different manufacturing strategies such as co-embossing and additive embossing are demonstrated for joining the materials with diverse compositions and functionalities. Structures with distinct combinations of properties such as hydrophobic-hydrophilic, opaque-transparent, insulator-conductor, and nonmagnetic-ferromagnetic are produced using this approach. These anisotropic properties are further utilized for selective functionalization of Janus structures.

Thermomechanical Behavior of Molded Metallic Glass Nanowires.

Metallic glasses are disordered materials that offer the unique ability to perform thermoplastic forming operations at low thermal budget while preserving excellent mechanical properties such as high strength, large elastic strain limits, and wear resistance owing to the metallic nature of bonding and lack of internal defects. Interest in molding micro- and nanoscale metallic glass objects is driven by the promise of robust and high performance micro- and nanoelectromechanical systems and miniature energy conversion devices. Yet accurate and efficient processing of these materials hinges on a robust understanding of their thermomechanical behavior. Here, we combine large-scale thermoplastic tensile deformation of collections of Pt-based amorphous nanowires with quantitative thermomechanical studies of individual nanowires in creep-like conditions to demonstrate that superplastic-like flow persists to small length scales. Systematic studies as a function of temperature, strain-rate, and applied stress reveal the transition from Newtonian to non-Newtonian flow to be ubiquitous across the investigated length scales. However, we provide evidence that nanoscale specimens sustain greater free volume generation at elevated temperatures resulting in a flow transition at higher strain-rates than their bulk counterparts. Our results provide guidance for the design of thermoplastic processing methods and methods for verifying the flow response at the nanoscale.

Metallic glass nanostructures: fabrication, properties, and applications.

Remarkable progress has been made in fabrication and characterization of metal nanostructures because of their crucial role in energy conversion, nanophotonics, nanoelectronics, and biodiagnostics. Less emphasis has been placed on the synthesis of nanostructures from metallic alloys, which are better suited than elemental metals for certain applications such as fuel-cell catalysts. The main challenges in fabrication of alloy nanostructures are controlling their chemical stoichiometry, crystal structures, and shapes because of anisotropic nucleation and growth rates. These limitations can be overcome by using metallic glasses (amorphous metal alloys) which are isotropic and provide additional control handles through their tunable compositions and degree of crystallinity. Here, we review the recent developments in fabrication and characterization of metallic glass (MG) nanostructures. The focus is on sub-micron structures synthesized by unconventional thermoplastic techniques. A concept of self-assembly is introduced for fashioning functional structures using MG nanostructures as building blocks. The article concludes with a brief discussion about unique properties and prospective applications of MG nanostructures.

Critical fictive temperature for plasticity in metallic glasses.

A long-sought goal in metallic glasses is to impart ductility without conceding their strength and elastic limit. The rational design of tough metallic glasses, however, remains challenging because of the inability of existing theories to capture the correlation between plasticity, composition and processing for a wide range of glass-forming alloys. Here we propose a phenomenological criterion based on a critical fictive temperature, T(fc), which can rationalize the effect of composition, cooling rate and annealing on room-temperature plasticity of metallic glasses. Such criterion helps in understanding the widespread mechanical behaviour of metallic glasses and reveals alloy-specific preparation conditions to circumvent brittleness.

Bulk metallic glass: the smaller the better.

Bulk metallic glasses (BMGs) are strong, highly elastic, and resistant to wear but still find limited utility due to their macroscopic brittle nature, high costs, and difficulty of processing, particularly when complex shapes are desired. These drawbacks can be mitigated when BMGs are used in miniature parts (< 1 cm), an application which takes advantage of BMGs' enhanced plasticity at small length scales as well the insignificant material cost associated with such parts. As an alternative to traditional metal processing techniques, thermoplastic forming (TPF)-based microfabrication methods have been developed which can process some BMGs like plastics. In this article, we discuss the properties and fabrication of BMGs on minuscule length scales to explore their prospective application in small-scale devices.

Bulk metallic glass nanowire architecture for electrochemical applications.

Electrochemical devices have the potential to pose powerful solutions in addressing rising energy demands and counteracting environmental problems. However, currently, these devices suffer from meager performance due to poor efficiency and durability of the catalysts. These suboptimal characteristics have hampered widespread commercialization. Here we report on Pt(57.5)Cu(14.7)Ni(5.3)P(22.5) bulk metallic glass (Pt-BMG) nanowires, whose novel architecture and outstanding durability circumvent the performance problems of electrochemical devices. We fabricate Pt-BMG nanowires using a facile and scalable nanoimprinting approach to create dealloyed high surface area nanowire catalysts with high conductivity and activity for methanol and ethanol oxidation. After 1000 cycles, these nanowires maintain 96% of their performance-2.4 times as much as conventional Pt/C catalysts. Their properties make them ideal candidates for widespread commercial use such as for energy conversion/storage and sensors.