Metal–organic framework (MOF) glasses are a fascinating new class of materials, yet their prosperity has been impeded by the scarcity of known examples and limited vitrification methods. In the work described in this report, we applied synergistic stimuli of vapor hydration and thermal dehydration to introduce structural disorders in interpenetrated dia -net MOF, which facilitate the formation of stable super-cooled liquid and quenched glass. The material after stimulus has a glass transition temperature (T g) of 560 K, far below the decomposition temperature of 695 K. When heated, the perturbed MOF enters a super-cooled liquid phase that is stable for a long period of time (>104 s), across a broad temperature range (26 K), and has a large fragility index of 83. Quenching the super-cooled liquid gives rise to porous MOF glass with maintained framework connectivity, confirmed by EXAFS and PDF analysis. This method provides a fundamentally new route to obtain glassy materials from MOFs that cannot be melted without causing decomposition.

Relaxation processes are decisive for many physical properties of amorphous materials. For amorphous phasechange materials (PCMs) used in nonvolatile memories, relaxation processes are, however, difficult to characterize because of the lack of bulk samples. Here, instead of bulk samples, we use powder mechanical spectroscopy for powder samples to detect the prominent excess wings-a characteristic feature of -relaxations-in a series of amorphous PCMs at temperatures below glass transitions. By contrast, -relaxations are vanishingly small in amorphous chalcogenides of similar composition, which lack the characteristic features of PCMs. This conclusion is corroborated upon crossing the border from PCMs to non-PCMs, where -relaxations drop substantially. Such a distinction implies that amorphous PCMs belong to a special kind of covalent glasses whose locally fast atomic motions are preserved even below the glass transitions. These findings suggest a correlation between -relaxation and crystallization kinetics of PCMs, which have technological implications for phase-change memory functionalities.

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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