Kinetics of high density functional polymer nanocomposite formation by tuning enthalpic and entropic barriers.

High density functional polymer nanocomposites (PNCs) with high degree of dispersion have recently emerged as novel materials for various thermo-mechanical, optical and electrical applications. The key challenge is to attain a high loading while maintaining reasonable dispersion to attain maximum possible benefits from the functional nanoparticle additives. Here, we report a facile method to prepare polymer grafted nanoparticle (PGNP)-based high density functional polymer nanocomposites using thermal activation of a high density PGNP monolayer to overcome entropic or enthalpic barriers to insertion of PGNPs into the underlying polymer films. We monitor the temperature-dependent kinetics of penetration of a high density PGNP layer and correlate the penetration time to the effective enthalpic/entropic barriers. The experimental results are corroborated by coarse-grained molecular dynamics simulations. Repeated application of the methodology to insert nanoparticles by appropriate control over temperature, time and graft-chain properties can lead to enhanced densities of loading in the PNC. Our method can be engineered to produce a wide range of high density polymer nanocomposite membranes for various possible applications including gas separation and water desalination.

Microscopic Dynamics of Liquid-Liquid Phase Separation and Domain Coarsening in a Protein Solution Revealed by X-Ray Photon Correlation Spectroscopy.

While the interplay between liquid-liquid phase separation (LLPS) and glass formation in biological systems is highly relevant for their structure formation and thus function, the exact underlying mechanisms are not well known. The kinetic arrest originates from the slowdown at the molecular level, but how this propagates to the dynamics of microscopic phase domains is not clear. Since with diffusion, viscoelasticity, and hydrodynamics, distinctly different mechanisms are at play, the dynamics needs to be monitored on the relevant time and length scales and compared to theories of phase separation. Using x-ray photon correlation spectroscopy, we determine the LLPS dynamics of a model protein solution upon low temperature quenches and find distinctly different dynamical regimes. We observe that the early stage LLPS is driven by the curvature of the free energy and speeds up upon increasing quench depth. In contrast, the late stage dynamics slows down with increasing quench depth, fingerprinting a nearby glass transition. The dynamics observed shows a ballistic type of motion, implying that viscoelasticity plays an important role during LLPS. We explore possible explanations based on the Cahn-Hilliard theory with nontrivial mobility parameters and find that these can only partially explain our findings.

Kinetics of Network Formation and Heterogeneous Dynamics of an Egg White Gel Revealed by Coherent X-Ray Scattering.

The kinetics of heat-induced gelation and the microscopic dynamics of a hen egg white gel are probed using x-ray photon correlation spectroscopy along with ultrasmall-angle x-ray scattering. The kinetics of structural growth reveals a reaction-limited aggregation process with a gel fractal dimension of ≈2 and an average network mesh size of ca. 400 nm. The dynamics probed at these length scales reveals an exponential growth of the characteristic relaxation times followed by an intriguing steady state in combination with a compressed exponential correlation function and a temporal heterogeneity. The degree of heterogeneity increases with decreasing length scale. We discuss our results in the broader context of experiments and models describing attractive colloidal gels.

Engineering interfacial entropic effects to generate giant viscosity changes in nanoparticle embedded polymer thin films.

Thin polymer and polymer nanocomposite (PNC) films are being extensively used as advanced functional coating materials in various technological applications. Since it is widely known that various properties of these thin films, especially their thermo-mechanical behavior, can be considerably different from the bulk depending on the thickness as well as interaction with surrounding media, it is imperative to study these properties directly on the films. However, quite often, it becomes difficult to perform these measurements reliably due to a dearth of techniques, especially to measure mechnical or transport properties like the viscosity of thin polymer or PNC films. Here, we demonstrate a new method to study the viscosity of PNC thin films using atomic force microscopy based force-distance spectroscopy. Using this method we investigated viscosity and the glass transition, Tg, of PNC thin films consisting of polymer grafted nanoparticles (PGNPs) embedded in un-entangled homopolymer melt films. The PGNP-polymer interfacial entropic interaction parameter, f, operationally controlled through the ratio of grafted and matrix molecular weight, was systematically tuned while maintaining good dispersion even at very high PGNP loadings, φ. We observed both a significant reduction (low f) and giant enhancement (high f) in the viscosity of the PNC thin films with the effect becoming more prominent with increasing φ. Significantly, none of the established theoretical models for viscosity changes observed earlier in suspensions or polymer nanocomposites can explain the observed viscosity variation. Our results thus not only demonstrate the tunability of the interfacial entropic effect to facilitate a dramatic change in the viscosity of PNC coatings, which could be of great utility in various applications of these materials, but also suggest a new regime of viscosity variation in athermal PNC films indicating the possible need for a new theoretical model.

Thermal stability and dynamics of soft nanoparticle membranes: role of entropy, enthalpy and membrane compressibility.

Nanoparticle based ultra-thin membranes have been shown to have remarkable mechanical properties while also possessing novel electrical, optical or magnetic properties, which could be controlled by tailoring properties at the level of individual nanoparticles. Since in most cases the ultra-thin membranes are coupled to some substrates, the role of membrane-substrate interactions, apart from nanoparticle-nanoparticle interactions become very crucial in understanding their mechanical and thermal stability, as well as their plethora of applications. However, systematic studies in this direction have been conspicuously absent. Here we report thermal stability and the corresponding microscopic dynamics of polymer supported ultra-thin membranes comprising of self-assembled, ordered grains of polymer grafted nanoparticles having tunable mechanical properties. The initially ordered membranes show distinct pathways for temperature induced disordering depending on membrane flexibility as well as on interfacial entropic and enthalpic interactions with the underlying polymer thin film. We also observe contrasting temperature dependence of microscopic dynamics of these membranes depending on whether the graft polymer-substrate polymer interactions are predominantly entropic or enthalpic in nature. Our results suggest that apart from their varied applications, the soft nanoparticle-polymer hybrid membranes are a playground for rich physics involving subtle entropic and enthalpic effects along with the nanoparticles softness, which eventually determine their thermo-mechanical stability.

Nanoparticle-polymer interfacial layer properties tune fragility and dynamic heterogeneity of athermal polymer nanocomposite films.

Enthalpic interactions at the interface between nanoparticles and matrix polymers are known to influence various properties of the resultant polymer nanocomposites (PNC). For athermal PNCs, consisting of grafted nanoparticles embedded in chemically identical polymers, the role and extent of the interface layer (IL) interactions in determining the properties of the nanocomposites are not very clear. Here, we demonstrate the influence of the interfacial layer dynamics on the fragility and dynamical heterogeneity (DH) of athermal and glassy PNCs. The IL properties are altered by changing the grafted to matrix polymer size ratio, f, which in turn changes the extent of matrix chain penetration into the grafted layer, λ. The fragility of PNCs is found to increase monotonically with increasing entropic compatibility, characterised by increasing λ. Contrary to observations in most polymers and glass formers, we observe an anti-correlation between the dependence on IL dynamics of fragility and DH, quantified by the experimentally estimated Kohlrausch-Watts-Williams parameter and the non-Gaussian parameter obtained from simulations.

Transient Cooperative Processes in Dewetting Polymer Melts.

We compare the high velocity dewetting behavior, at elevated temperatures, of atactic polystyrene (aPS) and isotactic polystyrene (iPS) films, with the zero shear bulk viscosity (η_{bulk}) of aPS being approximately ten times larger than iPS. As expected, for aPS the apparent viscosity of the films (η_{f}) derived from high-shear dewetting is less than η_{bulk}, displaying a shear thinning behavior. Surprisingly, for iPS films, η_{f} is always larger than η_{bulk}, even at about 50 °C above the melting point, with η_{f}/η_{bulk} following an Arrhenius behavior. The corresponding activation energy of ∼160±10 kJ/mol for iPS films suggests a cooperative motion of segments which are aligned and agglomerated by fast dewetting.

Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States.

Langmuir polymers films (LPFs) frequently form nonequilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(γ-benzyl-L-glutamate)(PBLG), visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films.

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature.

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Suspensions of polymer-grafted nanoparticles with added polymers-Structure and effective pair-interactions.

We present the results of combined experimental and theoretical (molecular dynamics simulations and integral equation theory) studies of the structure and effective interactions of suspensions of polymer grafted nanoparticles (PGNPs) in the presence of linear polymers. Due to the absence of systematic experimental and theoretical studies of PGNPs, it is widely believed that the structure and effective interactions in such binary mixtures would be very similar to those of an analogous soft colloidal material-star polymers. In our study, polystyrene-grafted gold nanoparticles with functionality f = 70 were mixed with linear polystyrene (PS) of two different molecular weights for obtaining two PGNP:PS size ratios, ξ = 0.14 and 2.76 (where, ξ = Mg/Mm, Mg and Mm being the molecular weights of grafting and matrix polymers, respectively). The experimental structure factor of PGNPs could be modeled with an effective potential (Model-X), which has been found to be widely applicable for star polymers. Similarly, the structure factor of the blends with ξ = 0.14 could be modeled reasonably well, while the structure of blends with ξ = 2.76 could not be captured, especially for high density of added polymers. A model (Model-Y) for effective interactions between PGNPs in a melt of matrix polymers also failed to provide good agreement with the experimental data for samples with ξ = 2.76 and high density of added polymers. We tentatively attribute this anomaly in modeling the structure factor of blends with ξ = 2.76 to the questionable assumption of Model-X in describing the added polymers as star polymers with functionality 2, which gets manifested in both polymer-polymer and polymer-PGNP interactions especially at higher fractions of added polymers. The failure of Model-Y may be due to the neglect of possible many-body interactions among PGNPs mediated by matrix polymers when the fraction of added polymers is high. These observations point to the need for a new framework to understand not only the structural behavior of PGNPs but also possibly their dynamics and thermo-mechanical properties as well.

Fast Processing Affects the Relaxation of Polymers: The Slow Arrhenius Process Can Probe Stress at the Molecular Level.

Polymer materials are commonly processed at rates higher than those at which their molecules spontaneously reach equilibrium conditions. The resulting nonequilibrium conformations might significantly affect the mechanical behavior and the shelf time of the final products. To understand how processing-properties relations work, we investigated the impact of spin coating, an archetypical method to fabricate thin polymer layers. By using a geometry in which nonequilibrium conformations are frozen over sufficiently long experimental times, we could identify how molecular relaxation is affected by fast preparation methods. We find that while the (α-)segmental relaxation is not affected by the rate at which films are processed, the intensity of the slow Arrhenius process (SAP), a relaxation mechanism active both above and below the glass transition, can be used as a probe of the degree of mechanical stress experienced by the material.

Variation in glass transition temperature of polymer nanocomposite films driven by morphological transitions.

We report the variation of glass transition temperature in supported thin films of polymer nanocomposites, consisting of polymer grafted nanoparticles embedded in a homopolymer matrix. We observe a systematic variation of the estimated glass transition temperature T(g), with the volume fraction of added polymer grafted nanoparticles. We have correlated the observed T(g) variation with the underlying morphological transitions of the nanoparticle dispersion in the films. Our data also suggest the possibility of formation of a low-mobility glass or gel-like layer of nanoparticles at the interface, which could play a significant role in determining T(g) of the films provided.

Re-entrant behavior in dynamics of binary mixtures of soft hybrid nanocolloids and homopolymers.

We present results of measurements of temperature and wavevector dependent dynamics in binary mixtures of soft polymer grafted nanoparticles and linear homopolymers. We find evidence of melting of the dynamically arrested state of the soft nanocolloids with addition of linear polymers followed by a re-entrant slowing down of the dynamics with further increase in polymer density, depending on the size ratio, δ, of the polymers and the nanocolloids. For higher δ the re-entrant behavior is not observed, even for the highest added polymer density, explored here. Possible explanation of the observed dynamics in terms of the presence of a double-glass phase is provided.

Communication: Unusual dynamics of hybrid nanoparticles and their binary mixtures.

We present the results on the evolution of microscopic dynamics of hybrid nanoparticles and their binary mixtures as a function of temperature and wave vector. We find unexpectedly a nonmonotonic dependence of the structural relaxation time of the nanoparticles as a function of the morphology. In binary mixtures of two of the largest nanoparticles studied, we observe re-entrant vitrification as a function of the volume fraction of the smaller nanoparticle, which is unusual for such high diameter ratio. Possible explanation for the observed behavior is provided.

Segmental Rearrangements Relax Stresses in Nonequilibrated Polymer Films.

We probed the relaxation of preparation-induced residual stresses in nonequilibrated polymer films through dewetting experiments. While we observed fast relaxations at temperatures close to or below the glass transition, at elevated temperatures these relaxation times were orders of magnitude longer than the reptation time. Intriguingly, applying appropriate scaling of preparation conditions allowed us to present all relaxation times, including published data, from various complementary experiments on a single master curve exhibiting an Arrhenius-type behavior. The corresponding activation energy (75 ± 10 kJ/mol) is similar to values obtained for the relaxation of segments in polystyrene. The observed long relaxation times suggest that residual stresses, a consequence of nonequilibrium conformations inherited from preparation, relax via concerted rearrangements of many segments.

Viscosity and fragility of confined polymer nanocomposites: a tale of two interfaces.

Viscosity and fragility are key parameters determining the processability and thermo-mechanical stability of glassy polymers and polymer nanocomposites (PNCs). In confined polymers, these parameters are largely dominated by the long relaxation times of the polymers adsorbed at the substrate-polymer interface. On the other hand, for polymer nanocomposites, the interface layer (IL) between the nanoparticles and the surrounding matrix chains often control not only the morphology and dispersion but also various parameters like viscosity and glass transition temperature. Confined PNCs, hence, present a unique opportunity to study the interplay of these two independent interfacial effects. Here, we report the results of X-ray scattering based dynamics measurements of PNC thin films, with a two IL width, unraveling the subtle interplay of these two interfaces on the measured viscosity and fragility. Coupled with coarse-grained molecular dynamics (MD) simulations, our experimental results demonstrate that the viscosity of the PNC films increases with both the IL width and the thickness of the polymer layer adsorbed at the substrate interface. However, while both pristine PS and PNCs with a higher IL width become stronger glasses, as estimated by their fragility, the PNC with a lower IL width shows an increase in fragility with increasing confinement. Our results suggest a novel method to control thermo-mechanical properties and stability of PNC coatings by independently controlling the two interfacial effects in athermal glassy PNCs.

Tuning relaxation dynamics and mechanical properties of polymer films of identical thickness.

Using dewetting as a characterization tool, we demonstrate that physical properties of thin polymer films can be regulated and tuned by employing variable processing conditions. For different molecular weights, the variable behavior of polystyrene films of identical thickness, prepared along systematically altered pathways, became predictable through a single parameter P, defined as the ratio of time required over time available for the equilibration of polymers. In particular, preparation-induced residual stresses, the corresponding relaxation times as well as the rupture probability of such films (of identical thickness) varied by orders of magnitude following scaling relations with P. Our experimental findings suggest that we can predictably enhance properties and hence maximize the performance of thin polymer films via appropriately chosen processing conditions.

Time Allowed for Equilibration Quantifies the Preparation Induced Nonequilibrium Behavior of Polymer Films.

Performance and properties of materials may strongly depend on processing conditions. This is particularly so for polymers, which often have relaxation times much longer than the processing times and therefore may adopt preparation dependent nonequilibrated molecular conformations that potentially cause novel properties. However, so far it was not possible to predictably and quantitatively relate processing steps and resulting properties of polymer films. Here, we demonstrate that the behavior of polymer films, probed through dewetting, can be tuned by controlling preparation pathways, defined through a dimensionless parameter [Formula: see text], which is the appropriate preparation time normalized with the characteristic relaxation time of the polymer. We revealed scaling relations between [Formula: see text] and the amount of preparation-induced residual stresses, the corresponding relaxation time, and the probability of film rupture. Intriguingly, films of the same thickness exhibited hole nucleation densities and subsequent dewetting kinetics differing by up to an order of magnitude, indicating possibilities to adjust the desired properties of polymer films by preparing them in appropriate ways.

Confinement enhances dispersion in nanoparticle-polymer blend films.

Polymer nanocomposites constitute an important class of materials whose properties depend on the state of dispersion of the nanoparticles in the polymer matrix. Here we report the first observations of confinement-induced enhancement of dispersion in nanoparticle-polymer blend films. Systematic variation in the dispersion of nanoparticles with confinement for various compositions and matrix polymer chain dimensions has been observed. For fixed composition, strong reduction in glass transition temperature, Tg, is observed with decreasing blend-film thickness. The enhanced dispersion occurs without altering the polymer-particle interactions and seems to be driven by enhanced matrix-chain orientation propensity and a tendency to minimize the density gradients within the matrix. This implies the existence of two different mechanisms in polymer nanocomposites, which determines their state of dispersion and glass transition.