Since their discovery in the 1960s, metallic glasses have continuously attracted much interest across the physics and materials science communities. In the forefront are their unique properties, which hold the alluring promise of broad application in fields as diverse as medicine, environmental science and engineering. However, a major obstacle to their wide-spread commercial use is their inherent temporal instability arising from underlying relaxation processes that can dramatically alter their physical properties. The result is a physical aging process which can bring about degradation of mechanical properties, namely through embrittlement and catastrophic mechanical failure. Understanding and controlling the effects of aging will play a decisive role in our on-going endeavor to advance the use of metallic glasses as structural materials, as well as in the more general comprehension of out-of-equilibrium dynamics in complex systems. This review presents an overview of the current state of the art in the experimental advances probing physical aging and relaxation processes in metallic glasses. Similarities and differences between other hard and soft matter glasses are highlighted. The topic is discussed in a multiscale approach, first presenting the key features obtained in macroscopic studies, then connecting them to recent novel microscopic investigations. Particular emphasis is put on the occurrence of distinct relaxation processes beyond the main structural process in viscous metallic melts and their fate upon entering the glassy state, trying to disentangle results and formalisms employed by the different groups of the glass-science community. A microscopic viewpoint is presented, in which physical aging manifests itself in irreversible atomic-scale processes such as avalanches and intermittent dynamics, ascribed to the existence of a plethora of metastable glassy states across a complex energy landscape. Future experimental challenges and the comparison with recent theoretical and numerical simulations are discussed as well.

https://iopscience.iop.org/article/10.1088/1361-648X/aa9964/pdf

Relaxation processes and physical aging in metallic glasses.

Via fast differential scanning calorimetry using an Au-based glass as an example, we show that metallic glasses should be classified into two types of amorphous/monolithic glass. The first type, termed self-doped glass (SDG), forms quenched-in nuclei or nucleation precursors upon cooling, whereas in the so-called chemically homogeneous glass (CHG) no quenched-in structures are found. For the Au-based glass investigated, the critical cooling and heating rates for the SDG are 500 K s−1 and 20,000 K s−1, respectively; for the CHG they are 4000 K s−1 and 6000 K s−1. The similarity in the critical rates for CHG, so far not reported in literature, and CHG’s tendency towards stochastic nucleation underline the novelty of this glass state. Identifying different types of metallic glass, as is possible by advanced chip calorimetry, and comparing them with molecular and polymeric systems may help to elaborate a more generalized glass theory and improve metallic glass processing. Quantifying the complexity of glass formation is difficult because it usually requires cooling at enormous speeds. Here, the authors use fast differential scanning calorimetry to classify metallic glasses into two types, one with quenched-in nuclei and one without.

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Existence of multiple critical cooling rates which generate different types of monolithic metallic glass.

The performance of polymeric semiconductors is profoundly affected by the thermodynamic state of its crystalline and amorphous fractions and how they affect the optoelectronic properties While intense research has been conducted on the crystalline features, fundamental understanding of the amorphous fraction(s) is still lacking Here, we employ fast scanning calorimetry to provide insights on the glass transition of the archetypal conjugated polymer poly(3-hexylthiophene) (P3HT) According to the conceptual definition of the glass transition temperature (Tg), that is, the temperature marking the crossover from the melt in metastable equilibrium to the nonequilibrium glass, an enthalpy relaxation should be observed by calorimetry when the glass is aged below Tg Thus, we are able to identify the enthalpy relaxations of mobile and rigid amorphous fractions (MAF and RAF, respectively) of P3HT and to determine their respective Tg Our work moreover highlights that the RAF should be included in structural mod

Direct Calorimetric Observation of the Rigid Amorphous Fraction in a Semiconducting Polymer

One puzzling phenomenon in glass physics is the so-called 'shadow glass transition' which is an anomalous heat-absorbing process below the real glass transition and influences glass properties. However, it has yet to be entirely characterized, let alone fundamentally understood. Conventional calorimetry detects it in limited heating rates. Here, with the chip-based fast scanning calorimetry, we study the dynamics of the shadow glass transition over four orders of magnitude in heating rates for 24 different hyper-quenched metallic glasses. We present evidence that the shadow glass transition correlates with the secondary (β) relaxation: (i) The shadow glass transition and the β relaxation follow the same temperature-time dependence, and both merge with the primary relaxation at high temperature. (ii) The shadow glass transition is more obvious in glasses with pronounced β relaxation, and vice versa; their magnitudes are proportional to each other. Our findings suggest that the shadow glass transition signals the thermodynamics of β relaxation in hyper-quenched metallic glasses.

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Shadow glass transition as a thermodynamic signature of β relaxation in hyper-quenched metallic glasses.

Nanocalorimetry: Door opened for in situ material characterization under extreme non-equilibrium conditions

Hierarchical aging pathways and reversible fragile-to-strong transition upon annealing of a metallic glass former

Many glass-formers exhibit phase transitions between two distinct liquid states. For some metallic glass-formers, the liquid-liquid transition is experimentally found in the supercooled liquid at intermediate temperature between the melting point and the glass transition temperature Tg. We report here on a liquid-liquid transition in an ultra-viscous metallic glass-former, accessed during long-time annealing. This study is conducted on the Au49Cu26.9Si16.3Ag5.5Pd2.3 composition with a liquid-liquid transition temperature slightly lower than Tg. The consequence is that the high-temperature kinetically fragile liquid freezes into the glass during conventional processing and the underlying liquid-liquid transition is thus accessed by the system during annealing below Tg. Upon reheating, the reverse transformation is observed by calorimetry. This conclusion is supported by a broad collection of complementary laboratory and synchrotron-based techniques, such as differential- and fast- scanning calorimetry, and x-ray photon correlation spectroscopy. Our findings support the big-picture proposed by Angell that liquids with different fragility occupy different flanks of an underlying order-disorder transition. Furthermore, our multiscale analysis reveals the existence of multiple decays of the enthalpy recovery, which is reflected in the observed microscopic ordering and aging mechanism of the glass through distinct stationary regimes interconnected by abrupt dynamical aging regimes.

Lisa Schmitt

Papers

Hierarchical aging pathways and reversible fragile-to-strong transition upon annealing of a metallic glass former

Activation energy spectrum for relaxation and polyamorphism in an ultra-viscous metallic glass former