Thermoplasticity of metallic glasses: Processing and applications

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Abstract

Owing to their extremely low shear viscosity and fragility, bulk metallic glasses (BMGs) are envisioned as new net-shaping material replacing conventionally used crystalline metals for various applications. The first part of this review describes the general technique and kinetics of thermoplastic forming. The second part elaborates on the thermal processing capability of metallic glasses from atomic- to meter-scale. The micro-/nano-structure obtained after various quenching rates followed by temperature, time and heating rate dependent thermoplastic forming is described in the third section. The deformation behavior and flow kinetics of BMGs in terms of composition, mold features, and applied conditions are elaborated in the fourth section. The variation of volume and enthalpy at the supercooled liquid region, strength retention of metallic glasses compared to other conventional metals and alloys, and kinetics of liquid fragility are given in the fifth section. Finite element modeling and molecular dynamics simulations of high-temperature deformation in BMGs are presented in the sixth part. Thermally-formed BMGs used for different applications, including energy, biomedical and micro-optics, are presented in the final part. Altogether, this review provides an overview of shaping capabilities and modifications in the macro-scale properties and short-to-medium range order of BMGs upon thermoplastic forming.

Introduction

Bulk metallic glasses (BMGs) are a new class of amorphous materials composed of (transition) metals or the combination of metals and metalloids. After the discovery of the first metallic glass (MG), Au75Si25, in 1960 [1] intense focus has been directed towards understanding the origins of glass forming ability (GFA) and the necessary criteria for identifying alloy compositions with high GFA [2]. The glass forming ability of a melt is evaluated in terms of the critical cooling rate, Rc, for glass formation, which is the minimum cooling rate necessary to keep the melt amorphous without precipitation of any crystals during solidification [3]. In general, higher degrees of chemical complexity are required for metallic alloys to exhibit good GFA; however ternary alloys have also been reported to have high enough GFA to form BMGs [4].

Extremely low shear viscosity and fragility, along with their grain- and defect-free amorphous structure as a secondary reason, grant a unique combination of mechanical, thermal and chemical properties. The yield strength of these materials, varying between 1 and 5 GPa, and even exceeding for some of the Co–, CoFe- and Ir-based alloys [5], [6], [7], is higher than for many conventional alloys such as steel and copper, titanium, aluminum alloys, etc., used in industry [8], [9]. In composites derived from bulk metallic glasses, which contain homogenously dispersed crystals, a world record-breaking yield strength with excellent elasticity has been achieved (Hugonoit elastic limit of 4 % and corresponding stress of 12.5 GPa [10]). Furthermore, very high fracture toughness values (>200 MPa m−1/2) similar to ductile low-carbon steels have been achieved for Pd-based BMGs [11]. The surface and corrosion properties of these alloy systems under extreme environments are quite promising as well [12], [13]. In addition to their appealing mechanical and chemical properties, sluggish atomic diffusion results in high thermal stability [14]. The sluggish atomic diffusion also enables the characterization of various thermophysical properties of the undercooled liquid such as specific heat [15], [16], [17], diffusion [18], [19], [20], viscosity [21], [22], [23], emissivity [24], [25], Curie temperature [26], [27], [28] and crystallization [29], [30], [31], [32].

These materials are nowadays discussed for green energy applications owing to their long-term hydrogen storage capabilities [33], [34], [35] or electrocatalytic hydrogen activity [36], [37], [38], [39], [40], [41], and are considered for use as hydrogen sensors [42], [43], [44] and permeation membranes [45], [46], [47]. Besides, BMGs have a wide range of potential application fields in biomedicine ranging from orthopedic, cardiovascular to dental implants and fillers, surgical tools and glucose sensors [48], [49], [50], [51], [52], [53], [54], [55]. Other potential applications of BMGs are wastewater treatment, sensors/actuators, optics, magnetics, acoustics, as well as in kinetic penetrators and satellite applications [56], [57], [58], [59], [60], [61], [62], [63].

Their facile processability can diversify the possibility of using metallic glasses in nowadays devices and systems at elevated temperatures under low applied pressures and moderate strain rates. This can be achieved by combining higher strength than crystalline metal alloys at room temperature with the easy deformability of polymers in their supercooled liquid region. Many different discovered metallic glass-forming systems, including (Cu)Zr-, Mg-, Pt-, Pd-, Au-, Ti-, La-, Fe(Co)-alloys and others in assorted dimensions and scales, have been successfully turned into more complex geometries using the concept of thermoplastic forming (TPF). A wide range of TPF-processing methods has been developed for BMGs, which have dramatically increased the range of geometries that can be net-shaped [64], including some previously unachievable shapes with any metal processing method [65], [66]. In recent years, particular focus of TPF of BMGs has been on micro- and nanoscale applications owing to their structural homogeneity and facile fabrication on multiple length scales [67], [68], [69], [70].

In this contribution, we present a broad overview in terms of recent research findings for thermoplastically formable metallic glasses. We will then focus on the potential and newest application fields of metallic glasses produced by the TPF process.

Section snippets

Technique and kinetics of thermoplastic forming

This chapter gives a brief overview of the process conditions of thermoplastic forming and how BMGs can be characterized in terms of their deformation kinetics. The key concepts introduced are Newtonian viscous flow (NVF), fragility, supercooled liquid region (SCLR), time–temperature-transformation (TTT) curves, and parameters for evaluating the formability.

The study of “supercooling” or “undercooling” of glass forming materials has excelled our knowledge on nucleation and growth of crystals in

Summary & future outlook

The low viscosity and Newtonian viscous flow of metallic glasses at their supercooled liquid regions allow net-shaping of objects at very close tolerances. For this reason, the thermoplastic forming of metallic glasses can be applied to ten orders of magnitude length scales, from replication of atomically smooth surfaces to meter-sized objects. The gradual drop in viscosity above the glass transition is determined by the composition and structural state of the metallic glass, where nano to

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors are grateful for the financial support of the European Research Council under the Advanced Grant “INTELHYB–Next generation of complex metallic materials in intelligent hybrid structures” (Grant ERC-2013-ADG-340025) and under the ERC Proof of Concept Grant TriboMetGlass (grant ERC-2019-PoC-862485), the Ministry of Science and Higher Education of the Russian Federation in the framework of the Increase Competitiveness Program of MISiS (support project for young research engineers,

Dr. Baran Sarac received his BSc from Middle East Technical University, MSc and PhD from Yale University, Department of Mechanical Engineering and Materials Science. He was a postdoc at Helmholtz Zentrum Geesthacht and IFW Dresden, and between 2016-2020 he acted as a scientific coordinator of an ERC Advanced Grant – Intelhyb in the field of advanced alloy systems at Erich Schmid Institute of Materials Science – Austrian Academy of Sciences. Since 2018 he is the project leader of a bilateral

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    Dr. Baran Sarac received his BSc from Middle East Technical University, MSc and PhD from Yale University, Department of Mechanical Engineering and Materials Science. He was a postdoc at Helmholtz Zentrum Geesthacht and IFW Dresden, and between 2016-2020 he acted as a scientific coordinator of an ERC Advanced Grant – Intelhyb in the field of advanced alloy systems at Erich Schmid Institute of Materials Science – Austrian Academy of Sciences. Since 2018 he is the project leader of a bilateral FWF-ANR project which includes development, thermoplasticity and investigation of new-generation Ti-based metallic glasses for biomedical applications. He has authored a book and a number of publications in the fields of synthesis, thermal forming techniques, characterization, and biomedical and energy applications of metallic glasses and other advanced metallic alloys in prestigious peer-reviewed journals.

    Prof. Jürgen Eckert is Director of the Erich Schmid Institute of Materials Science of the Austrian Academy of Sciences and Head of the Department Materials Physics at Montanuniversität Leoben, Austria. Before he was Director of the Institute for Complex Materials at the Leibniz-Institute for Solid State and Materials Research Dresden and Full Professor at Dresden University of Technology, Germany. His major research areas are materials physics, metastable materials, processing of micro/nanostructured alloys, structure and property correlations and structural and physical properties of advanced materials. He is coauthor of more than 1400 scientific papers and has presented numerous invited and plenary talks at international conferences. He has received prestigious prizes and grants including Gottfried Wilhelm Leibniz-Prize 2009 of the German Research Foundation, ERC-Advanced Grant of the European Research Council – Intelhyb (2013) and THERMEC 2021 Distinguished Award.

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    Adjunct with National University of Science and Technology «MISiS», Leninsky Prosp., 4, 119049 Moscow, Russia.

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