Glass-forming Polymers Research Articles

Characterizing Rotational Dynamics and Heterogeneity via Single-Molecule Intensity Measurements.

Dynamic heterogeneity in glassy systems has typically been characterized at the single-molecule level by extracting rotational relaxation time scales from linear dichroism (LD) collected via two orthogonally polarized channels. However, in such measurements, localization precision is diminished due to photons lost relative to collection in a single detection channel. This poses challenges in characterizing rotational and translational dynamics simultaneously, as translational measurements require high localization precision. In this paper, we present a method for extracting rotational dynamics of glassy systems at the single-molecule level from intensity fluctuations of fluorescent probe molecules in a wide-field configuration without the use of a polarizing optical component. Through numerical analysis, we show that LD and intensity measurements probing rotational dynamics report similar, approximately second-order rotational correlation decays even at low signal to noise. Thus, within the assumptions of small, isotropic rotations, LD and intensity autocorrelation analysis should provide identical information on the time scale and heterogeneity of rotational dynamics. We then present experimental results that validate this numerical result, with direct comparison of LD and intensity-based approaches across probe molecules in both polymeric and small-molecule glass formers as well as across optical configurations. Our results demonstrate moderate correlation on a per-probe basis between rotational time scales obtained from both approaches, with deviations consistent with those expected in a dynamically heterogeneous system. We envision that this easily accessible strategy will be of use across disciplines for characterizing single-molecule rotational dynamics in limited signal situations and/or when high-precision localization is required.

The thermo-optical coefficient as an alternative probe for the structural arrest of polymeric glass formers

The most important, yet independent susceptibilities to characterize the canonical glass transition include the thermal expansion, the specific heat and the shear modulus. At the glass transition, all these susceptibilities show a step-like behaviour as a function of temperature. However, in principle, different susceptibilities provide different perspectives on the glass transition. Due to the effect of sample history and considerable kinetic influences on the thermal glass transition behaviour, the best way to evaluate these different perspectives is to investigate them simultaneously. In this publication, different perspectives on the dynamical freezing process are obtained by a single experimental method: Temperature-modulated optical refractometry (TMOR). TMOR is used to simultaneously investigate the dynamic thermal expansion and, indirectly, the shear viscosity of a model polymer, both contributing to the thermo-optical coefficient. It will be discussed how this thermo-optical property couples to the structural arrest designated as one of the characteristics of the solidification process of polymers.

Nature of Subdiffusion Crossover in Molecular and Polymeric Glassformers.

A crossover from a non-Gaussian to Gaussian subdiffusion has been observed ubiquitously in various polymeric and molecular glassformers. We have developed a framework that generalizes the fractional Brownian motion model to incorporate non-Gaussian features by introducing a jump kernel. We illustrate that the non-Gaussian fractional Brownian motion model accurately characterizes the subdiffusion crossover. From the solutions of the non-Gaussian fractional Brownian motion model, we gain insights into the nature of van Hove self-correlation in non-Gaussian subdiffusive regime, which is found to exhibit exponential tails, providing first such experimental evidence in molecular glassformers. The validity of the model is supported by comparison with incoherent quasielastic neutron scattering data obtained from several molecular and polymeric glassformers.

Parallel Emergence of Rigidity and Collective Motion in a Family of Simulated Glass-Forming Polymer Fluids

Parallel Emergence of Rigidity and Collective Motion in a Family of Simulated Glass-Forming Polymer Fluids

Advances in the generalized entropy theory of polymer glass formation

Advances in the generalized entropy theory of polymer glass formation

Determination of Cooperativity Length in a Glass-Forming Polymer.

To describe the properties of glass-forming liquids, the concepts of a cooperativity length or the size of cooperatively rearranging regions are widely employed. Their knowledge is of outstanding importance for the understanding of both thermodynamic and kinetic properties of the systems under consideration and the mechanisms of crystallization processes. By this reason, methods of experimental determination of this quantity are of outstanding importance. Proceeding in this direction, we determine the so-called cooperativity number and, based on it, the cooperativity length by experimental measurements utilizing AC calorimetry and quasi-elastic neutron scattering (QENS) at comparable times. The results obtained are different in dependence on whether temperature fluctuations in the considered nanoscale subsystems are either accounted for or neglected in the theoretical treatment. It is still an open question, which of these mutually exclusive approaches is the correct one. As shown in the present paper on the example of poly(ethyl methacrylate) (PEMA), the cooperative length of about 1 nm at 400 K and a characteristic time of ca. 2 μs determined from QENS coincide most consistently with the cooperativity length determined from AC calorimetry measurements if the effect of temperature fluctuations is incorporated in the description. This conclusion indicates that-accounting for temperature fluctuations-the characteristic length can be derived by thermodynamic considerations from the specific parameters of the liquid at the glass transition and that temperature does fluctuate in small subsystems.

Glass formation and dynamics of model polymer films with one versus two active interfaces.

Polymers and other glass-forming liquids can exhibit profound alterations in dynamics in the nanoscale vicinity of interfaces, over a range appreciably exceeding that of typical interfacial thermodynamic gradients. The understanding of these dynamical gradients is particularly complicated in systems with internal or external nanoscale dimensions, where a gradient nucleated at one interface can impinge on a second, potentially distinct, interface. To better understand the interactions that govern system dynamics and glass formation in these cases, here we simulate the baseline case of a glass-forming polymer film, over a wide range of thickness, supported on a dynamically neutral substrate that has little effect on nearby dynamics. We compare these results to our prior simulations of freestanding films. Results indicate that dynamical gradients in our simulated systems, as measured based upon translational relaxation, are simply truncated when they impinge on a secondary surface that is locally dynamically neutral. Altered film behavior can be described almost entirely by gradient effects down to the thinnest films probed, with no evidence for finite-size effects sometimes posited to play a role in these systems. Finally, our simulations predict that linear gradient overlap effects in the presence of symmetric dynamically active interfaces yield a non-monotonic variation of the whole free standing film stretching exponent (relaxation time distribution breadth). The maximum relaxation time distribution breadth in simulation is found at a film thickness of 4-5 times the interfacial gradient range. Observation of this maximum in experiment would provide an important validation that the gradient behavior observed in simulation persists to experimental timescales. If validated, observation of this maximum would potentially also enable determination of the dynamic gradient range from experimental mean-film measurements of film dynamics.

Thermal Perturbations at Crystal Nucleation in Glass-Forming Liquids

Understanding the processes occurring during the nanocrystallization of glass-forming liquids is important for creating artificial nanostructures for various applications. In this article, local thermal perturbations in supercooled glass-forming liquids and polymers during the nucleation of a crystalline phase are studied. To describe the thermal response of supercooled glass-forming liquids, an integro-differential heat equation with dynamic heat capacity is used. We have found that the effect of the dynamic heat capacity is significant for fast local thermal perturbations that arise in the early stages of crystal nucleation in glass-forming liquids and polymers. It has been established that local temperature perturbations during the nucleation of crystals in silicate glasses and polymers can change the nucleation rate by 2–5 orders of magnitude. The knowledge gained can be useful for the technology of artificial microstructures and advanced materials.

Heat Transfer Processes at Early Stages of Crystal Nucleation in Glass-Forming Materials and Polymers

Heat Transfer Processes at Early Stages of Crystal Nucleation in Glass-Forming Materials and Polymers

Relating dynamic free volume to cooperative relaxation in a glass-forming polymer composite.

There are a variety of complementary descriptions of the temperature dependence of the structural relaxation time τ in glass-forming materials, which we interpret positively as suggesting an underlying unified description. We examine the inter-relation between the string model, an outgrowth of the Adam and Gibbs approach that emphasizes collective particle exchange motion, and the localization model, which emphasizes the volume explored by particles in their caged states, a kind of dynamic "free volume." Each model of liquid dynamics is described by a limited set of parameters that must be interrelated if both descriptions simultaneously describe the relaxation behavior. We pursue the consequences of this idea by performing coarse-grained molecular simulations of polymer melts with additives of variable size and interaction strength with the polymer matrix, thereby significantly altering the relaxation of the composite material. Both the string and localization models describe our relaxation time data well, and a comparison of the model parameters allows us to relate the local caging scale ⟨u2⟩ (the Debye-Waller parameter) to the entropy of activation for molecular rearrangements in the string model, thereby developing a bridge between these seemingly disparate approaches to liquid dynamics.

Temperature Dependence of Structural Relaxation in Glass-Forming Liquids and Polymers.

Understanding the microscopic mechanism of the transition of glass remains one of the most challenging topics in Condensed Matter Physics. What controls the sharp slowing down of molecular motion upon approaching the glass transition temperature Tg, whether there is an underlying thermodynamic transition at some finite temperature below Tg, what the role of cooperativity and heterogeneity are, and many other questions continue to be topics of active discussions. This review focuses on the mechanisms that control the steepness of the temperature dependence of structural relaxation (fragility) in glass-forming liquids. We present a brief overview of the basic theoretical models and their experimental tests, analyzing their predictions for fragility and emphasizing the successes and failures of the models. Special attention is focused on the connection of fast dynamics on picosecond time scales to the behavior of structural relaxation on much longer time scales. A separate section discusses the specific case of polymeric glass-forming liquids, which usually have extremely high fragility. We emphasize the apparent difference between the glass transitions in polymers and small molecules. We also discuss the possible role of quantum effects in the glass transition of light molecules and highlight the recent discovery of the unusually low fragility of water. At the end, we formulate the major challenges and questions remaining in this field.

Self-assembled nanocomposites of high water content and load-bearing capacity.

Biological tissues, such as cartilage, tendon, ligament, skin, and plant cell wall, simultaneously achieve high water content and high load-bearing capacity. The high water content enables the transport of nutrients and wastes, and the high load-bearing capacity provides structural support for the organisms. These functions are achieved through nanostructures. This biological fact has inspired synthetic mimics, but simultaneously achieving both functions has been challenging. The main difficulty is to construct nanostructures of high load-bearing capacity, characterized by multiple properties, including elastic modulus, strength, toughness, and fatigue threshold. Here we develop a process that self-assembles a nanocomposite using a hydrogel-forming polymer and a glass-forming polymer. The process separates the polymers into a hydrogel phase and a glass phase. The two phases arrest at the nanoscale and are bicontinuous. Submerged in water, the nanocomposite maintains the structure and resists further swelling. We demonstrate the process using commercial polymers, achieving high water content, as well as load-bearing capacity comparable to that of polyethylene. During the process, a rubbery stage exists, enabling us to fabricate objects of complex shapes and fine features. We conduct further experiments to discuss likely molecular origins of arrested phase separation, swell resistance, and ductility. Potential applications of the nanocomposites include artificial tissues, high-pressure filters, low-friction coatings, and solid electrolytes.

Cyclic Olefin Copolymers (COC)—Excellent Glass Formers with Low Dynamic Fragility

AbstractApplications of cyclic olefin copolymers (COC) are manifold, and developing a complete understanding of the characteristics of the glass transition behavior of these materials is essential to their processing and use in a variety of those applications. Fast scanning calorimetry is employed to investigate the glass transition of three commercial TOPAS COCs of different norbornene content between 37 and 54 mol% at cooling rates varying from 0.01 to 100 000 K s−1. The glass transition temperatures as a function of cooling rate are determined as limiting fictive temperatures from reheating scans at 100 000 K s−1. The data, covering seven orders of magnitude in cooling rate, allows the determination of the dynamic fragilities. The dynamic fragilities of TOPAS 6013, 6015, and 8007 are in the range of 50–60 and increase with increasing norbornene content. Compared to literature data of other polymers, the dynamic fragilities are rather low, and the COCs are classified as relatively strong glass formers. In other words, relating this information to processability, they have a relatively large “working range” and are classified as “long” glasses. Such classification, borrowed from glass making (blowing) technologies, may also help to describe the processability of polymeric glass formers in general.

Correlation between fragility and free volume void size at glass transition temperature

Despite the tremendous endeavors devoted to exploiting the nature of glass transition, the factors that control the steepness index of viscosity near glass transition, that is, fragility, remain unclear. In this study, we demonstrate that, for polymeric and small molecular weight organic glass formers, fragility increases upward with increasing size of the free volume void at the glass transition temperature. This changing trend indicates that fragility is governed by the properties of the segments or molecular clusters in the free volume void rather than by the properties of the entire polymer chains. The physics behind the relationship between fragility and free volume void at the glass transition temperature is consistent with the physics behind the relationship between fragility and the molecular weight as well as the mechanics of the relationship between fragility and size of the cooperative units. This relationship also provides new insights into the understanding of the nature of the glass transition of polymeric and small molecular weight organic glass formers.

Isochronal superpositioning of the caged dynamics, the α, and the Johari-Goldstein β relaxations in metallic glasses.

The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time τα(T, P) constant (i.e., isochronal superpositioning) has been well established in molecular and polymeric glass-formers. Not known is whether the frequency dispersion or time dependence of the faster processes including the caged molecule dynamics and the Johari-Goldstein (JG) β relaxation possesses the same property. Experimental investigation of this issue is hindered by the lack of an instrument that can cover all three processes. Herein, we report the results from the study of the problem utilizing molecular dynamics simulations of two different glass-forming metallic alloys. The mean square displacement 〈Δr2t〉, the non-Gaussian parameter α2t, and the self-intermediate scattering function Fsq,t at various combinations of T and P were obtained over broad time range covering the three processes. Isochronal superpositioning of 〈Δr2t〉, α2t, and Fsq,t was observed over the entire time range, verifying that the property holds not only for the α relaxation but also for the caged dynamics and the JG β relaxation. Moreover, we successfully performed density ρ scaling of the time τα2,maxT,P at the peak of α2t and the diffusion coefficient D(T, P) to show both are functions of ργ/T with the same γ. It follows that the JG β relaxation time τβ(T, P) is also a function of ργ/T since τα2,maxT,P corresponds to τβ(T, P).

Residual changes and thickness effects in glass-forming polymer thin films after solvent vapor annealing

Residual solvent in polymer coatings caused by solvent vapor annealing (SVA) may be used as an indicator of the SVA effectivity for block-copolymer self-assembly and other applications. To analyze the residual changes, temperature-programmed desorption (TPD) technique has been applied to 6–200 nm thick glassy polymer coatings processed by SVA. This method is based on the film thickness contraction and expansion measurements by ellipsometry in vacuum as the temperature of the sample ramps up. The measurements are corrected for the polymer thermal expansion. The polymers used are polystyrene, poly (methyl methacrylate), and poly (2-vinyl pyridine). The TPD curves exhibit up to 2 distinct desorption peaks. One peak appears in the vicinity of the film's glass transition temperature Tg. This feature shows up only if the coating has reached a solvent-induced glass transition during the preceding vapor annealing. The other desorption event is a broad feature appearing at the temperatures below Tg. This peak is observed even for the coatings without previous solvent vapor exposure, although the SVA enhances the effect. The magnitude of the desorption effect corresponds to 1% of the residual solvent content or less for about 30 nm thick films. The desorption demonstrates a clear thickness effect and becomes more pronounced for thinner films, but not exceeding a few % of the residual solvent in 5–8 nm thick coatings. It is supposed that the desorption event in the Tg vicinity is mainly caused by the loss of the solvent or voids from the polymer due to the increased molecular mobility, while the low temperature feature is mostly a desorption of residual gases from the sample surface. Application of the TPD data and sorption-desorption isotherms to the optimization of the SVA procedure and creating a process window plot is demonstrated.

Experimental Tests of a Theoretically Predicted Noncausal Correlation between Dynamics and Thermodynamics in Glass-forming Polymer Melts

The connection between slow activated relaxation in glass-forming liquids and various equilibrium thermodynamic properties remains intensely debated. The microscopic elastically collective nonlinea...

A Dynamically Correlated Network Model for the Collective Dynamics in Glass-Forming Molecular Liquids and Polymers.

The non-Arrhenius behavior of segmental dynamics in glass-forming liquids is one of the most profound mysteries in soft matter physics. In this article, we propose a dynamically correlated network (DCN) model to understand the growing behavior of dynamically correlated regions during cooling, which leads to the viscous slowdown of supercooled liquids. The fundamental concept of the model is that the cooperative region of collective motions has a network structure that consists of string-like parts, and networks of various sizes interpenetrate each other. Each segment undergoes dynamical coupling with its neighboring segments via a finite binding energy. Monte Carlo simulations showed that the fractal dimension of the DCNs generated at different temperatures increased and their size distribution became broader with decreasing temperature. The segmental relaxation time was evaluated based on a power law with four different exponents for the activation energy of rearrangement with respect to the DCN size. The results of the present DCN model are consistent with the experimental results for various materials of molecular and polymeric liquids.

Influence of Tacticity on the Glass-Transition Dynamics of Poly(methyl methacrylate) (PMMA) under Elevated Pressure and Geometrical Nanoconfinement

The physicochemical properties of polymers can be modified by spatial configuration. Here, dielectric spectroscopy (DS) was employed to investigate the effect of the tacticity on the glass-transition dynamics of confined polymer films. We have also carried out dielectric relaxation studies at ambient and elevated pressure conditions. High-pressure measurements provide information on the sensitivity of the glass-transition dynamics to density changes, which can be helpful to better understand the confinement effect. For our study, we have chosen a glass-forming polymer, poly(methyl methacrylate) (PMMA), with two different tacticities (isotactic and syndiotactic) and an approximately equal molecular weight. We have shown that the segmental relaxation for the bulk syndiotactic PMMA is observed at a higher temperature range compared to the bulk isotactic PMMA. The experimental data analysis has also revealed that the molecular order influences the behavior of the polymer under increased pressure. The glass-transition dynamics of isotactic PMMA is more sensitive to the pressure/density changes than syndiotactic PMMA. Finally, we have also demonstrated that tacticity has a significant impact on the segmental dynamics of the confined polymer films. Syndiotactic PMMA has a stronger interaction with the substrate than isotactic PMMA, which is indicated by the higher amount of irreversibly adsorbed polymer chains. For this reason, the segmental dynamics of s-PMMA thin films follows the bulk behavior. In contrast, for i-PMMA, the confinement effects are pronounced, and the glass-transition dynamics accelerate with the reduction of the thickness of thin films.

New Experimental Evidence for Thermodynamic Links to the Kinetic Fragility of Glass-Forming Polymers

New Experimental Evidence for Thermodynamic Links to the Kinetic Fragility of Glass-Forming Polymers