Glass Formation Behavior Research Articles

The Time-Temperature Superposition of Polymeric Rubber Gels Treated by Means of the Mode-Coupling Theory.

Viscoelastic relaxation measurements on styrene-butadiene rubbers (SBRs) doped with carbon nanotube (CNT) at different concentrations around the sol-gel transition show the time-temperature superposition (TTS). This process is described in terms of the mode coupling theory (MCT) approach to viscoelasticity by considering the frequency behavior of the loss modulus E″(ω) and showing that the corresponding TTS is linked to ω1/2 decay. From the analysis of the obtained data, we observe that the interaction between SBRs and CNT determines different levels of decay according to their concentration. Systems with the lowest CNT concentration are only characterized in the studied T-range by their fragile glass-forming behavior. However, at a specific temperature TL, those with the highest CNT concentration show a crossover towards pure Arrhenius that, according to the MCT, indicates the presence of kinetic glass transition (KGT), where system response functions are characterized by scaling behaviors.

The influence of molecular shape on glass-forming behavior in a minimalist trimer model.

In this study, we employed molecular dynamics simulations to probe the influence of molecular morphological changes on the dynamic behavior of a model consisting of trimer molecules. This model, comprising a chain of three particles, facilitates the exploration of variations in the internal angle between these particles. Our findings highlight the significant impact of molecular conformation: systems with more linear conformations, characterized by larger internal angles, exhibit relaxation times several orders of magnitude greater than their counterparts with smaller internal angles. Furthermore, we delve into the role of angular interaction rigidity, uncovering a pronounced deceleration in dynamics and an increase in dynamic heterogeneity as rigidity escalates. This model not only provides insights into azobenzene-type systems but also sets the stage for subsequent research into the microscopic nuances of related systems, with potential extensions to composite systems.

Combined Mixing and Dynamical Origins of Tg Alterations Near Polymer–Polymer Interfaces

The extent to which altered glass formation behavior in block copolymers and layered polymers results from local compositional mixing vs from longer-ranged dynamical correlations has long been unresolved. Here, we perform molecular dynamics simulations at model polymer–polymer interfaces to understand the relative roles of these mechanisms. Results indicate a crossover from the high-χ regime, where near-interface Tg alterations are driven purely by dynamical gradient effects, to the low-χ regime, where both local mixing and dynamical correlations play a role. Observed Tg gradient ranges are asymmetric, exceed the range of composition gradients, and modestly grow with decreasing χ. These results provide new insight into the design of nanostructured polymers with targeted local dynamics. They also emphasize an apparent dichotomy between many studies, including ours, pointing toward Tg gradient ranges on the order of 10 nm, and a second set of studies reporting on longer ranges up to hundreds of nanometers.

Q-dependent collective relaxation dynamics of glass-forming liquid Ca0.4K0.6(NO3)1.4 investigated by wide-angle neutron spin-echo

The relaxation behavior of glass formers exhibits spatial heterogeneity and dramatically changes upon cooling towards the glass transition. However, the underlying mechanisms of the dynamics at different microscopic length scales are not fully understood. Employing the recently developed wide-angle neutron spin-echo spectroscopy technique, we measured the Q-dependent coherent intermediate scattering function of a prototypical ionic glass former Ca0.4K0.6(NO3)1.4, in the highly viscous liquid state. In contrast to the structure modulated dynamics for Q < 2.4 Å−1, i.e., at and below the structure factor main peak, for Q > 2.4 Å−1, beyond the first minimum above the structure factor main peak, the stretching exponent exhibits no temperature dependence and concomitantly the relaxation time shows smaller deviations from Arrhenius behavior. This finding indicates a change in the dominant relaxation mechanisms around a characteristic length of 2π/(2.4 Å−1) ≈ 2.6 Å, below which the relaxation process exhibits a temperature independent distribution and more Arrhenius-like behavior.

Thermo-crosslinkable molecular glasses towards the low k materials at high frequency

Two molecular glasses having allyl side chains and thermo-crosslinkable benzocyclobutene (BCB) groups have been successfully synthesized. These molecules display good solubility in common organic solvents and show a typical glass-forming behavior of having no melting point and keeping a complete amorphous state. The thermally cured molecular glasses exhibit low dielectric constant (Dk) and dielectric loss (Df) at 10 GHz, as well as low water uptake (Wa) even when they are immersed in boiling water for 72 h. Among them, a fluoro-containing molecule exhibits the best properties, showing Dk of 2.53, Df of 1.93 × 10−3 and Wa of 0.19%, respectively, indicating that fluoro groups can efficiently improve the dielectric properties of the molecules. A controlling test indicates that the allyl side chains make the molecules possessing glass-forming properties.

Memory Effect and Crystallization of (R, S)-2-Chloromandelic Acid Glass.

(R, S)-2-Chloromandelic acid, which can crystallize in racemic crystals (forms α and β) or a conglomerate (form γ), has been studied for its glass-forming behavior. Below the glass transition temperature, samples of the title compound crack into pieces. Correlation plots of DSC results have been used to investigate what determines the cracking and its occurrence temperature. We found that the latter is influenced by the polymorph from which the melt state has been obtained, showing that a certain memory of the previous crystalline phase persists in the undercooled melt. Moreover, this residual structure could be eliminated by elongating the annealing period or increasing the annealing temperature. Investigation using broadband dielectric spectroscopy confirmed such a memory effect. Finally, we studied the role of cracking in the control of the crystallization. In contrast with previous literature on other glass-forming molecular systems, we verified that the crystallization upon reheating is not impacted by the occurrence of cracks in the glassy state. This observation challenges the current views on polymorphic crystallization from organic glasses.

Engineering of new Mg-based glassy compositions by a computational intelligence model

Due to a wide variety of physical parameters for designing metallic glasses (MGs), it is difficult to fabricate them without performing time-consuming and costly experiments. To tackle this problem, we proposed an artificial intelligence approach, i.e. machine learning model, to predict the inherent features of MGs with promising alloying compositions. As a case study, Mg-Cu-Y ternary system was examined for engineering potential MG compositions. To make better glass forming ability (GFA), some elements such as Ag, Pd and Ni were minor added into the ternary system. The results indicated that the added elements significantly change the glass formation behavior of ternary system and shift the maximum GFA based on their interaction with the elemental constitutes of alloying composition.

A New Glass Forming Electrolyte Based on Lithium Glycerolate

The study of the interplay between structure and conductivity in lithium-conducting electrolytes is a pivotal point for the development of future secondary batteries [1]. The use of Glycerol as a low molecular weight component in electrolytes is particularly interesting due to its glass-forming behavior and low glass transition temperature (-78.5°C). In addition, a high flexibility of the alkyl backbone chain and the well-known capability of oxygen functionalities to coordinate lithium cations make Glycerol very appealing as ion-conducting media as well as building block to obtain hybrid polymer electrolytes [2].On this basis a family of eleven electrolytes based on Lithium Glycerolate with general formula C3H8-xO3Lix, where 0 ≤ x ≤ 1, is prepared and investigated [3]. In these electrolytes the Glycerolate (C3H8-xO3 x-) component acts as a large and flexible macro-anion which is able to provide a high single-ion conductivity to the material (8.36∙10-5 S∙cm-1 at 20°C and 1.55∙10-2 S∙cm-1 at 150°C for x = 0.25).Finally, the Glycerol∙∙∙Li+ interactions in these electrolytes are studied on T and x, with a particular reference to the detection of: a) macro-anion coordination sites; and b) the secondary structure of Glycerol chains. Insights on the long-range charge transfer mechanism and Glycerol relaxation events are also discussed.These studies are carried out by Inductively-Coupled Plasma Atomic Emission Spectroscopy, IR and Raman spectroscopies, DSC, TGA, and Broadband Electrical Spectroscopy.

Probing the Metrology and Chemistry Dependences of the Onset Condition of Strong “Nanoconfinement” Effects on Dynamics

Polymers in the nanoscale vicinity of interfaces exhibit a broad range of alterations in their dynamics and glass-formation behavior. A major goal in the study of these effects is to understand the...

A New Glass Forming Electrolyte Based on Lithium Glycerolate

The study of the interplay between structure and conductivity in lithium-conducting electrolytes is a pivotal point for the development of future secondary batteries [1]. The use of Glycerol as a low molecular weight component in electrolytes is particularly interesting due to its glass-forming behavior and low glass transition temperature (-78.5°C). In addition, a high flexibility of the alkyl backbone chain and the well-known capability of oxygen functionalities to coordinate lithium cations make Glycerol very appealing as ion-conducting media as well as building block to obtain hybrid polymer electrolytes [2].On this basis a family of eleven electrolytes based on Lithium Glycerolate with general formula C3H8-xO3Lix, where 0 ≤ x ≤ 1, is prepared and investigated [3]. In these electrolytes the Glycerolate (C3H8-xO3 x-) component acts as a large and flexible macro-anion which is able to provide a high single-ion conductivity to the material (8.36∙10-5 S∙cm-1 at 20°C and 1.55∙10-2 S∙cm-1 at 150°C for x = 0.25).Finally, the Glycerol∙∙∙Li+ interactions in these electrolytes are studied on T and x, with a particular reference to the detection of: a) macro-anion coordination sites; and b) the secondary structure of Glycerol chains. Insights on the long-range charge transfer mechanism and Glycerol relaxation events are also discussed.These studies are carried out by Inductively-Coupled Plasma Atomic Emission Spectroscopy, IR and Raman spectroscopies, DSC, TGA, and Broadband Electrical Spectroscopy.

Halogenated Metal–Organic Framework Glasses and Liquids

The synthesis of four novel crystalline zeolitic imidazolate framework (ZIF) structures using a mixed-ligand approach is reported. The inclusion of both imidazolate and halogenated benzimidazolate-derived linkers leads to glass-forming behavior by all four structures. Melting temperatures are observed to depend on both electronic and steric effects. Solid-state NMR and terahertz (THz)/far-IR demonstrate the presence of a Zn-F bond for fluorinated ZIF glasses. In situ THz/far-IR spectroscopic techniques reveal the dynamic structural properties of crystal, glass, and liquid phases of the halogenated ZIFs, linking the melting behavior of ZIFs to the propensity of the ZnN4 tetrahedra to undergo thermally induced deformation. The inclusion of halogenated ligands within metal-organic framework (MOF) glasses improves their gas-uptake properties.

Understanding, predicting, and tuning the fragility of vitrimeric polymers

Fragility is an empirical property that describes how abruptly a glass-forming material solidifies upon supercooling. The degree of fragility carries important implications for the functionality and processability of a material, as well as for our fundamental understanding of the glass transition. However, the microstructural properties underlying fragility still remain poorly understood. Here, we explain the microstructure-fragility link in vitrimeric networks, a novel type of high-performance polymers with unique bond-swapping functionality and unusual glass-forming behavior. Our results are gained from coarse-grained computer simulations and first-principles mode-coupling theory (MCT) of star-polymer vitrimers. We first demonstrate that the vitrimer fragility can be tuned over an unprecedentedly broad range, from fragile to strong and even superstrong behavior, by decreasing the bulk density. Remarkably, this entire phenomenology can be reproduced by microscopic MCT, thus challenging the conventional belief that existing first-principles theories cannot account for nonfragile behaviors. Our MCT analysis allows us to rationally identify the microstructural origin of the fragile-to-superstrong crossover, which is rooted in the sensitivity of the static structure factor to temperature variations. On the molecular scale, this behavior stems from a change in dominant length scales, switching from repulsive excluded-volume interactions to intrachain attractions as the vitrimer density decreases. Finally, we develop a simplified schematic MCT model which corroborates our microscopically founded conclusions and which unites our findings with earlier MCT studies. Our work sheds additional light on the elusive structure-fragility link in glass-forming matter and provides a first-principles-based platform for designing amorphous materials with an on-demand dynamic response.

Connecting 1D and 2D Confined Polymer Dynamics to Its Bulk Behavior via Density Scaling.

Under confinement, the properties of polymers can be much different from the bulk. Because of the potential applications in technology and hope to reveal fundamental problems related to the glass-transition, it is important to realize whether the nanoscale and macroscopic behavior of polymer glass-formers are related to each other in any simple way. In this work, we have addressed this issue by studying the segmental dynamics of poly(4-chlorostyrene) (P4ClS) in the bulk and upon geometrical confinement at the nanoscale level, in either one- (thin films on Al substrate) or two- (within alumina nanopores) dimensions. The results demonstrate that the segmental relaxation time, irrespective of the confinement size or its dimensionality, can be scaled onto a single curve when plotted versus ργ/T with the same single scaling exponent, γ = 3.1, obtained via measurements at high pressures in bulk. The implication is that the macro- and nanoscale confined polymer dynamics are intrinsically connected and governed by the same underlying rules.

Universal localization transition accompanying glass formation: insights from efficient molecular dynamics simulations of diverse supercooled liquids.

The origin of the precipitous dynamic arrest known as the glass transition is a grand open question of soft condensed matter physics. It has long been suspected that this transition is driven by an onset of particle localization and associated emergence of a glassy modulus. However, progress towards an accepted understanding of glass formation has been impeded by an inability to obtain data sufficient in chemical diversity, relaxation timescales, and spatial and temporal resolution to validate or falsify proposed theories for its physics. Here we first describe a strategy enabling facile high-throughput simulation of glass-forming liquids to nearly unprecedented relaxation times. We then perform simulations of 51 glass-forming liquids, spanning polymers, small organic molecules, inorganics, and metallic glass-formers, with longest relaxation times exceeding one microsecond. Results identify a universal particle-localization transition accompanying glass formation across all classes of glass-forming liquid. The onset temperature of non-Arrhenius dynamics is found to serve as a normalizing condition leading to a master collapse of localization data. This transition exhibits a non-universal relationship with dynamic arrest, suggesting that the nonuniversality of supercooled liquid dynamics enters via the dependence of relaxation times on local cage scale. These results suggest that a universal particle-localization transition may underpin the glass transition, and they emphasize the potential for recent theoretical developments connecting relaxation to localization and emergent elasticity to finally explain the origin of this phenomenon. More broadly, the capacity for high-throughput prediction of glass formation behavior may open the door to computational inverse design of glass-forming materials.

Influence of chain stiffness on the dynamical heterogeneity and fragility of polymer melts.

It is well accepted that stiffer polymers have higher glass transition temperatures. However, the influence of chain stiffness on the slow dynamics and dynamical heterogeneity when approaching the glass transition point is still not well understood. In this work, we investigate the influence of chain stiffness on the dynamic heterogeneity and fragility of supercooled polymer melts by using molecular dynamics simulation. The chain stiffness is tuned by varying the bending strength, and the diffusion and relaxation of polymer segments are studied. We find that the power law relation between the rescaled diffusion coefficient and the structural relaxation time does not change with changing chain stiffness, indicating similarities of glass-forming behavior of polymer melts with different chain stiffness. The dynamical heterogeneities are characterized by the non-Gaussian parameter and dynamic susceptibility, and the string-like cooperative motion is analyzed by the string-length. It is found that the non-Gaussian parameter and dynamic susceptibility characterize a different aspect of dynamical heterogeneities. Though both decreasing temperature and increasing bending strength lead to slower dynamics and growing dynamical heterogeneities, there is no simple superposition between temperature and bending strength. Our work may shed new light on the glass transition behavior of polymers with different chain stiffness.

Temperature-Independent Rescaling of the Local Activation Barrier Drives Free Surface Nanoconfinement Effects on Segmental-Scale Translational Dynamics near Tg.

Near-interface alterations in dynamics and glass formation behavior have been the subject of extensive study for the past two decades, both because of their practical importance and in the hope of revealing underlying correlation lengths underpinning glass transition more generally. Here we employ molecular dynamics simulations of thick films to demonstrate that these effects emerge, for segmental-scale translational dynamics at low temperature, from a temperature-independent rescaling of the local activation barrier. This rescaling manifests as a fractional power law decoupling relationship of local dynamics relative to the bulk, with a transition from a regime of weak decoupling at high temperatures to a regime of strong decoupling at low temperatures. The range of this effect saturates at low temperatures, with 90% of the surface perturbation in the barrier lost over a range of 12 segmental diameters. These findings reduce the phenomenology of Tg nanoconfinement effects to two properties-a position-dependent, temperature independent, barrier rescaling factor and an onset time scale-while substantially constraining the predictions required from any theoretical explanation of this phenomenon.

Structure and fragility in a macroscopic model of a glass-forming liquid based on a nonvibrating granular system

We studied glass transition in a nonvibrating granular system composed of magnetic steel beads under an unsteady magnetic field. In this model system, particle concentration and effective temperature can be changed independently. We analyzed several particle concentration cases. As concentration increases, the system goes from a fragile to a strong glass-forming liquid behavior and the regularity factor increases showing that the system becomes more regular. As the effective potential shows deeper wells, the fragility index decreases, and the regularity factor increases.

A New Glass-Forming Electrolyte Based on Lithium Glycerolate

The detailed study of the interplay between the physicochemical properties and the long-range charge migration mechanism of polymer electrolytes able to carry lithium ions is crucial in the development of next-generation lithium batteries. Glycerol exhibits a number of features (e.g., glass-forming behavior, low glass transition temperature, high flexibility of the backbone, and efficient coordination of lithium ions) that make it an appealing ion-conducting medium and a challenging building block in the preparation of new inorganic–organic polymer electrolytes. This work reports the preparation and the extensive investigation of a family of 11 electrolytes based on lithium glycerolate. The electrolytes have the formula C3H5(OH)3−x(OLi)x, where 0 ≤ x ≤ 1. The elemental composition is evaluated by inductively coupled plasma atomic emission spectroscopy. The structure and interactions are studied by vibrational spectroscopies (FT-IR and micro-Raman). The thermal properties are gauged by modulated differential scanning calorimetry and thermogravimetric analysis. Finally, insights on the long-range charge migration mechanism and glycerol relaxation events are investigated via broadband electrical spectroscopy. Results show that in these electrolytes, glycerolate acts as a large and flexible macro-anion, bestowing to the material single-ion conductivity (1.99 × 10−4 at 30 °C and 1.55 × 10−2 S∙cm−1 at 150 °C for x = 0.250).

Energy Renormalization Method for the Coarse-Graining of Polymer Viscoelasticity.

Developing temperature transferable coarse-grained (CG) models is essential for the computational prediction of polymeric glass-forming (GF) material behavior, but their dynamics are often greatly altered from those of all-atom (AA) models mainly because of the reduced fluid configurational entropy under coarse-graining. To address this issue, we have recently introduced an energy renormalization (ER) strategy that corrects the activation free energy of the CG polymer model by renormalizing the cohesive interaction strength ε as a function of temperature T, i.e., ε(T), thus semiempirically preserving the T-dependent dynamics of the AA model. Here we apply our ER method to consider-in addition to T-dependency-the frequency f-dependent polymer viscoelasticity. Through smallamplitude oscillatory shear molecular dynamics simulations, we show that changing the imposed oscillation f on the CG systems requires changes in ε values (i.e., ε(T, f)) to reproduce the AA viscoelasticity. By accounting for the dynamic fragility of polymers as a material parameter, we are able to predict ε(T, f) under coarse-graining in order to capture the AA viscoelasticity, and consequently the activation energy, across a wide range of T and f in the GF regime. Specifically, we showcase our achievements on two representative polymers of distinct fragilities, polybutadiene (PB) and polystyrene (PS), and show that our CG models are able to sample viscoelasticity up to the megahertz regime, which approaches state-of-the-art experimental resolutions, and capture results sampled via AA simulations and prior experiments.

Universal glass-forming behavior of in vitro and living cytoplasm

Physiological processes in cells are performed efficiently without getting jammed although cytoplasm is highly crowded with various macromolecules. Elucidating the physical machinery is challenging because the interior of a cell is so complex and driven far from equilibrium by metabolic activities. Here, we studied the mechanics of in vitro and living cytoplasm using the particle-tracking and manipulation technique. The molecular crowding effect on cytoplasmic mechanics was selectively studied by preparing simple in vitro models of cytoplasm from which both the metabolism and cytoskeletons were removed. We obtained direct evidence of the cytoplasmic glass transition; a dramatic increase in viscosity upon crowding quantitatively conformed to the super-Arrhenius formula, which is typical for fragile colloidal suspensions close to jamming. Furthermore, the glass-forming behaviors were found to be universally conserved in all the cytoplasm samples that originated from different species and developmental stages; they showed the same tendency for diverging at the macromolecule concentrations relevant for living cells. Notably, such fragile behavior disappeared in metabolically active living cells whose viscosity showed a genuine Arrhenius increase as in typical strong glass formers. Being actively driven by metabolism, the living cytoplasm forms glass that is fundamentally different from that of its non-living counterpart.