Experimental evidence of ß-relaxation and its structural origin in ZIF-62 glass.

Intrinsic relaxation processes determine the crucial properties of glass, yet their underlying mechanisms are far from well understood. The brand-new glass-forming metal-organic frameworks (MOFs) provide desirable opportunities for looking inside glass relaxation, especially the secondary ß-relaxation phenomenon and mechanism. For a representative zeolitic imidazolate framework-62 (ZIF-62) glass, reliable and fine powder mechanical spectroscopy was performed based on home-made mountings combined with a commercial dynamical mechanical analyzer. For the first time, ß-relaxation was observed in a MOF glass besides the primary α-relaxation. The pronounced ß-relaxation was well demonstrated by a number of characteristics including an excess wing and the full width at half maximum (W) of the α-relaxation peaks, which deviated from the time-temperature superposition. The stretched exponent ß of ZIF-62 glass is 0.71 in the supercooled region. The W of ZIF-62 glass is the maximum among all known glassy materials. The structural origin of α- and ß-relaxation can be attributed to an increase of density, as observed using nuclear magnetic resonance (NMR). A general linear and broad correlation of fragility and stretched exponent ß with W of the α-relaxation peaks was established. When compared with traditional glass-formers, the resulting principles indicate a shared origin for the stretched exponent ß, W, and ß-relaxation in the case of ZIF-62 glass. The presented findings offer an effective new method to explore the glass/liquid transition of MOF glasses, which helps to obtain a deeper insight into the hierarchical relaxation dynamics of the glass transition.

Multi-stage Transformations of a Cluster-Based Metal-Organic Framework: Perturbing Crystals to Glass-Forming Liquids that Re-Crystallize at High Temperature.

Glassy and liquid state metal-organic frameworks (MOFs) are emerging type of materials subjected to intense research for their rich physical and chemical properties. In this report, we obtained the first glassy MOF that involves metal-carboxylate cluster building units via multi-stage structural transformations. This MOF is composed of linear [Mn3 (COO)6 ] node and flexible pyridyl-ethenylbenzoic linker. The crystalline MOF was first perturbed by vapor hydration and thermal dehydration to give an amorphous state, which can go through a glass transition at 505 K into a super-cooled liquid. The super-cooled liquid state is stable through a wide temperature range of 40 K and has the largest fragility index of 105, giving a broad processing window. Remarkably, the super-cooled liquid can not only be quenched into glass, but also recrystallize into the initial MOF when heated to a higher temperature above 558 K. The mechanism of the multi-stage structural transformations was studied by systematic characterizations of in situ X-ray diffraction, calorimetry, rheological, spectroscopic and pair-distribution function analysis. These multi-stage transformations not only represent a rare example of high temperature coordinative recognition and self-assembly, but also provide new MOF processing strategy through crystal-amorphous-liquid-crystal transformations.

Vibration assisted glass-formation in zeolitic imidazolate framework.

A new glass forming method is essential for broadening the scope of liquid and glassy metal-organic frameworks due to the limitations of the conventional melt-quenching method. Herein, we show that in situ mechanical vibration can facilitate the framework melting at a lower temperature and produce glassy metal-organic frameworks (MOFs) with unique properties. Using zeolitic imidazolate framework (ZIF)-62 as a concept-proofing material, in situ mechanical vibration enables low-temperature melting at 653 K, far below its melting point (713 K). The resultant vibrated ZIF-62 glass exhibited a lower glass transition temperature of 545 K, improved gas accessible porosity, and pronounced short-to-medium range structures compared to the corresponding melt-quenched glass. We propose that vibration-facilitated surface reconstruction facilitates pre-melting, which could be the cause of the lowered melting temperature. The vibration assisted method represents a new general method to produce MOF glasses without thermal decomposition.

Synergistic Stimulation of Metal-Organic Frameworks for Stable Super-cooled Liquid and Quenched Glass.

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 (Tg) 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.

Uncovering ß-relaxations in amorphous phase-change materials.

Relaxation processes are decisive for many physical properties of amorphous materials. For amorphous phase-change 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 ß-relaxations-in a series of amorphous PCMs at temperatures below glass transitions. By contrast, ß-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 ß-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 ß-relaxation and crystallization kinetics of PCMs, which have technological implications for phase-change memory functionalities.

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

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 (ß) relaxation: (i) The shadow glass transition and the ß 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 ß relaxation, and vice versa; their magnitudes are proportional to each other. Our findings suggest that the shadow glass transition signals the thermodynamics of ß relaxation in hyper-quenched metallic glasses.

Predicting Complex Relaxation Processes in Metallic Glass.

Relaxation processes significantly influence the properties of glass materials. However, understanding their specific origins is difficult; even more challenging is to forecast them theoretically. In this study, using microseconds molecular dynamics simulations together with an accurate many-body interaction potential, we predict that an Al_{90}Sm_{10} metallic glass would have complex relaxation behaviors: In addition to the main (α) relaxation, the glass (i) shows a pronounced secondary (ß) relaxation at cryogenic temperatures and (ii) exhibits an anomalous relaxation process (α_{2}) accompanying α relaxation. Both of the predictions are verified by experiments. Computational simulations reveal the microscopic origins of relaxation processes: while the pronounced ß relaxation is attributed to the abundance of stringlike cooperative atomic rearrangements, the anomalous α_{2} process is found to correlate with the decoupling of the faster motions of Al with slower Sm atoms. The combination of simulations and experiments represents a first glimpse of what may become a predictive routine and integral step for glass physics.

Anomalous nonlinear damping in metallic glasses: Signature of elasticity breakdown.

Solid materials, whether crystalline or glasses, are characterized by their elasticity. Generally, elasticity is independent of the probing strain if it is not exceeding the yielding point. Here, by contrast, we experimentally capture a pronounced strain-dependent elasticity in metallic glasses, as manifested by nonlinear mechanical damping in the apparent elastic deformation regime (∼1/100 of the yielding strain). Normal damping behaviors recover at higher temperatures but still below the glass transition. Atomistic simulations reproduce these features and reveal that they could be related to avalanche-like local structural instabilities. Our findings demonstrate that the standard elasticity is not held for metallic glasses at low temperatures and plastic events can be triggered at small perturbations. These results are consistent with previous simulations of model glasses and a scenario of hierarchical free-energy landscape of mean-field theory.