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.

Sorption of CO2, CH4 and Their Mixtures in Amorphous Poly(2,6-dimethyl-1,4-phenylene)oxide (PPO).

Sorption of pure CO2 and CH4 and CO2/CH4 binary gas mixtures in amorphous glassy Poly(2,6-dimethyl-1,4-phenylene) oxide (PPO) at 35 °C up to 1000 Torr was investigated. Sorption experiments were carried out using an approach that combines barometry with FTIR spectroscopy in the transmission mode to quantify the sorption of pure and mixed gases in polymers. The pressure range was chosen to prevent any variation of the glassy polymer density. The solubility within the polymer of the CO2 present in the gaseous binary mixtures was practically coincident with the solubility of pure gaseous CO2, up to a total pressure of the gaseous mixtures equal to 1000 Torr and for CO2 mole fractions of ~0.5 mol mol-1 and ~0.3 mol mol-1. The Non-Equilibrium Thermodynamics for Glassy Polymers (NET-GP) modelling approach has been applied to the Non-Random Hydrogen Bonding (NRHB) lattice fluid model to fit the solubility data of pure gases. We have assumed here that no specific interactions were occurring between the matrix and the absorbed gas. The same thermodynamic approach has been then used to predict the solubility of CO2/CH4 mixed gases in PPO, resulting in a deviation lower than 9.5% from the experimental results for CO2 solubility.

The Hydrophobic Effect Studied by Using Interacting Colloidal Suspensions.

Interactions between nanoparticles (NPs) determine their self-organization and dynamic processes. In these systems, a quantitative description of the interparticle forces is complicated by the presence of the hydrophobic effect (HE), treatable only qualitatively, and due to the competition between the hydrophobic and hydrophilic forces. Recently, instead, a sort of crossover of HE from hydrophilic to hydrophobic has been experimentally observed on a local scale, by increasing the temperature, in pure confined water and studying the occurrence of this crossover in different water-methanol solutions. Starting from these results, we then considered the idea of studying this process in different nanoparticle solutions. By using photon correlation spectroscopy (PCS) experiments on dendrimer with OH terminal groups (dissolved in water and methanol, respectively), we show the existence of this hydrophobic-hydrophilic crossover with a well defined temperature and nanoparticle volume fraction dependence. In this frame, we have used the mode coupling theory extended model to evaluate the measured time-dependent density correlation functions (ISFs). In this context we will, therefore, show how the measured spectra are strongly dependent on the specificity of the interactions between the particles in solution. The observed transition demonstrates that just the HE, depending sensitively on the system thermodynamics, determines the hydrophobic and hydrophilic interaction properties of the studied nanostructures surface.

Modelling changes in glass transition temperature in polymer matrices exposed to low molecular weight penetrants.

Polymer matrices, when placed in contact with a fluid phase made of low molecular weight compounds, undergo a depression of their glass transition temperature (Tg) determined by the absorption of these compounds and the associated plasticization phenomena. Frequently, this effect is coupled with the mechanical action of the compressive stress exerted by the pressure of the fluid phase that, in contrast, promotes an increase in the Tg. This issue is relevant for technological and structural applications of composites with high-performance glassy polymer matrices, due to their significant impact on mechanical properties. We propose an approach to model and predict rubbery-glassy states maps of polymer-penetrant mixtures as a function of pressure and temperature based on the Gibbs-Di Marzio criterion. This criterion establishes that a 'thermodynamic' glass transition does occur when the configurational entropy of the system vanishes. Although questioned and criticized, this criterion constitutes a good practical approach to analyse changes of Tg and, in some way, reflects the idea of an 'entropy catastrophe' occurring at the glass transition. Several polymer-penetrant systems have been analysed modelling configurational entropy by means of the Non-Random Hydrogen Bond lattice fluid theory, able to cope with possible non-random mixing and occurrence of strong interactions. This article is part of the theme issue 'Ageing and durability of composite materials'.

Survey on Adsorption of Low Molecular Weight Compounds in Cu-BTC Metal-Organic Framework: Experimental Results and Thermodynamic Modeling.

This contribution aims at providing a critical overview of experimental results for the sorption of low molecular weight compounds in the Cu-BTC Metal-Organic Framework (MOF) and of their interpretation using available and new, specifically developed, theoretical approaches. First, a literature review of experimental results for the sorption of gases and vapors is presented, with particular focus on the results obtained from vibrational spectroscopy techniques. Then, an overview of theoretical models available in the literature is presented starting from semiempirical theoretical approaches suitable to interpret the adsorption thermodynamics of gases and vapors in Cu-BTC. A more detailed description is provided of a recently proposed Lattice Fluid approach, the Rigid Adsorbent Lattice Fluid (RALF) model. In addition, to deal with the cases where specific self- and cross-interactions (e.g., H-bonding, Lewis acid/Lewis base interactions) play a role, a modification of the RALF model, i.e., the RALFHB model, is introduced here for the first time. An extension of both RALF and RALFHB is also presented to cope with the cases in which the heterogeneity of the rigid adsorbent displaying a different kind of adsorbent cages is of relevance, as it occurs for the adsorption of some low molecular weight substances in Cu-BTC MOF.

Chemical Vapour Deposition Graphene-PMMA Nanolaminates for Flexible Gas Barrier.

Successful ways of fully exploiting the excellent structural and multifunctional performance of graphene and related materials are of great scientific and technological interest. New opportunities are provided by the fabrication of a novel class of nanocomposites with a nanolaminate architecture. In this work, by using the iterative lift-off/float-on process combined with wet depositions, we incorporated cm-size graphene monolayers produced via Chemical Vapour Deposition into a poly (methyl methacrylate) (PMMA) matrix with a controlled, alternate-layered structure. The produced nanolaminate shows a significant improvement in mechanical properties, with enhanced stiffness, strength and toughness, with the addition of only 0.06 vol% of graphene. Furthermore, oxygen and carbon dioxide permeability measurements performed at different relative humidity levels, reveal that the addition of graphene leads to significant reduction of permeability, compared to neat PMMA. Overall, we demonstrate that the produced graphene-PMMA nanolaminate surpasses, in terms of gas barrier properties, the traditional discontinuous graphene-particle composites with a similar filler content. Moreover, we found that the gas permeability through the nanocomposites departs from a monotonic decrease as a function of relative humidity, which is instead evident in the case of the pure PMMA nanolaminate. This work suggests the possible use of Chemical Vapour Deposition graphene-polymer nanolaminates as a flexible gas barrier, thus enlarging the spectrum of applications for this novel material.

The Interplay between the Theories of Mode Coupling and of Percolation Transition in Attractive Colloidal Systems.

In the recent years a considerable effort has been devoted to foster the understanding of the basic mechanisms underlying the dynamical arrest that is involved in glass forming in supercooled liquids and in the sol-gel transition. The elucidation of the nature of such processes represents one of the most challenging unsolved problems in the field of material science. In this context, two important theories have contributed significantly to the interpretation of these phenomena: the Mode-Coupling theory (MCT) and the Percolation theory (PT). These theories are rooted on the two pillars of statistical physics, universality and scale laws, and their original formulations have been subsequently modified to account for the fundamental concepts of Energy Landscape (EL) and of the universality of the fragile to strong dynamical crossover (FSC). In this review, we discuss experimental and theoretical results, including Molecular Dynamics (MD) simulations, reported in the literature for colloidal and polymer systems displaying both glass and sol-gel transitions. Special focus is dedicated to the analysis of the interferences between these transitions and on the possible interplay between MCT and PT. By reviewing recent theoretical developments, we show that such interplay between sol-gel and glass transitions may be interpreted in terms of the extended F13 MCT model that describes these processes based on the presence of a glass-glass transition line terminating in an A3 cusp-like singularity (near which the logarithmic decay of the density correlator is observed). This transition line originates from the presence of two different amorphous structures, one generated by the inter-particle attraction and the other by the pure repulsion characteristic of hard spheres. We show here, combining literature results with some new results, that such a situation can be generated, and therefore experimentally studied, by considering colloidal-like particles interacting via a hard core plus an attractive square well potential. In the final part of this review, scaling laws associated both to MCT and PT are applied to describe, by means of these two theories, the specific viscoelastic properties of some systems.

Tailoring Chitosan/LTA Zeolite Hybrid Aerogels for Anionic and Cationic Dye Adsorption.

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g-1, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.

Modelling Sorption Thermodynamics and Mass Transport of n-Hexane in a Propylene-Ethylene Elastomer.

Optimization of post polymerization processes of polyolefin elastomers (POE) involving solvents is of considerable industrial interest. To this aim, experimental determination and theoretical interpretation of the thermodynamics and mass transport properties of POE-solvent mixtures is relevant. Sorption behavior of n-hexane vapor in a commercial propylene-ethylene elastomer (V8880 VistamaxxTM from ExxonMobil, Machelen, Belgium) is addressed here, determining experimentally the sorption isotherms at temperatures ranging from 115 to 140 °C and pressure values of n-hexane vapor up to 1 atm. Sorption isotherms have been interpreted using a Non Random Lattice Fluid (NRLF) Equation of State model retrieving, from data fitting, the value of the binary interaction parameter for the n-hexane/V8880 system. Both the cases of temperature-independent and of temperature-dependent binary interaction parameter have been considered. Sorption kinetics was also investigated at different pressures and has been interpreted using a Fick's model determining values of the mutual diffusivity as a function of temperature and of n-hexane/V8880 mixture composition. From these values, n-hexane intra-diffusion coefficient has been calculated interpreting its dependence on mixture concentration and temperature by a semi-empiric model based on free volume arguments.

A Molecular Interpretation of the Dynamics of Diffusive Mass Transport of Water within a Glassy Polyetherimide.

The diffusion process of water molecules within a polyetherimide (PEI) glassy matrix has been analyzed by combining the experimental analysis of water sorption kinetics performed by FTIR spectroscopy with theoretical information gathered from Molecular Dynamics simulations and with the expression of water chemical potential provided by a non-equilibrium lattice fluid model able to describe the thermodynamics of glassy polymers. This approach allowed us to construct a convincing description of the diffusion mechanism of water in PEI providing molecular details of the process related to the effects of the cross- and self-hydrogen bonding established in the system on the dynamics of water mass transport.

Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime.

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences CP-CV, proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid "phases", namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the CP-CV isobars behaviors clearly support the existence of both a liquid-liquid transition and of a liquid-liquid critical point.

Morphology, molecular interactions and H2O diffusion in a poly(lactic-acid)/graphene composite: A vibrational spectroscopy study.

A composite system made of poly(l-lactic acid) (PLLA) and graphene nanoplatelets (GNP) was investigated by Raman and FTIR spectroscopy. Two compositions were prepared and characterized in comparison to the pristine polymer: they contained, respectively, 0.25 and 0.75 wt% of the nanofiller. The study was focused on the morphological properties of the system, and, in particular, on the level of dispersion and the homogeneity obtainable with the adopted preparation protocol. Furthermore, the possible molecular interactions taking place between the nanofiller and the polymer matrix were considered. Both the above issues were investigated by confocal Raman spectroscopy, with the aid of first-principle calculations to strengthen the spectral interpretation. Finally, the effect of the nanofiller on water diffusion was investigated by time-resolved FTIR spectroscopy, which provided accurate equilibrium and kinetic data, as well as molecular level information on the penetrant-to-substrate interactions. It was found that, for a 0.25 wt% composition, the adopted preparation protocol allowed us to achieve a dispersion at the level of single nanoplatelets, while for a 0.75 wt% composition, the GNP's aggregate into a co-continuous phase. PLLA/GNP interactions were detected by Raman spectroscopy, producing a detectable perturbation of the PLLA conformational equilibrium. Both the diffusivities and the equilibrium water uptake were found to decrease significantly by increasing the filler content.

Sorption Thermodynamics of CO2, H2O, and CH3OH in a Glassy Polyetherimide: A Molecular Perspective.

In this paper, the sorption thermodynamics of low-molecular-weight penetrants in a glassy polyetherimide, endowed with specific interactions, is addressed by combining an experimental approach based on vibrational spectroscopy with thermodynamics modeling. This modeling approach is based on the extension of equilibrium theories to the out-of-equilibrium glassy state. Specific interactions are accounted for in the framework of a compressible lattice fluid theory. In particular, the sorption of carbon dioxide, water, and methanol is illustrated, exploiting the wealth of information gathered at a molecular level from Fourier-transform infrared (FTIR) spectroscopy to tailor thermodynamics modeling. The investigated penetrants display a different interacting characteristic with respect to the polymer substrate, which reflects itself in the sorption thermodynamics. For the specific case of water, the outcomes from molecular dynamics simulations are compared with the results of the present analysis.

Retrieving acoustic energy densities and local pressure amplitudes in microfluidics by holographic time-lapse imaging.

The development of techniques able to characterize and map the pressure field is crucial for the widespread use of acoustofluidic devices in biotechnology and lab-on-a-chip platforms. In fact, acoustofluidic devices are powerful tools for driving precise manipulation of microparticles and cells in microfluidics in non-contact modality. Here, we report a full and accurate characterization of the movement of particles subjected to acoustophoresis in a microfluidic environment by holographic imaging. The particle displacement along the direction of the ultrasound wave propagation, coinciding with the optical axis, is observed and investigated. Two resonance frequencies are explored, varying for each the amplitude of the applied signal. The trajectories of individual tracers, accomplished by holographic measurements, are fitted with the theoretical model thus allowing the retrieval of the acoustic energy densities and pressure amplitudes through full holographic analysis. The absence of prior calibration, being independent of the object shape and the possibility of implementing automatic analysis make the use of holography very appealing for applications in devices for biotechnologies.

Modeling Retrograde Vitrification in the Polystyrene-Toluene System.

Atactic polystyrene, as reported in a recent contribution by our group, displays a marked change in glass transition when exposed to toluene vapor due to plasticization associated with vapor sorption within the polymer. The dependence of the glass transition temperature of the polymer-penetrant mixture on the pressure of toluene vapor is characterized by the so-called "retrograde vitrification" phenomenon, in that, at a constant pressure, a rubber to glass transition occurs by increasing the temperature. In this contribution, we have used a theoretical approach, based on the nonrandom lattice fluid thermodynamic model for the polymer-toluene mixture, to predict the state of this system, i.e., rubbery or glassy, as a function of fluid pressure and system temperature. The experimentally detectable glass transition is assumed to be a kinetically affected evidence of an underlying II order thermodynamic transition of the polymer mixture. On the basis of this hypothesis, the Gibbs-Di Marzio criterion, stating that equilibrium configurational entropy is zeroed at the glass transition, has been applied to locate the transition. The working set of equations consists of the expression of configurational entropy obtained from the adopted lattice fluid model equated to zero, coupled with the equation expressing the phase equilibrium between the polymer phase and the pure toluene vapor phase in contact and with the equations of state for the two phases. Theoretical predictions are in good qualitative and quantitative agreement with the experimental results previously obtained gravimetrically performing "dynamic" sorption experiments, which represent a neat example of the occurrence of so-called "type IV" glass transition temperature vs pressure behavior. The peculiar retrograde vitrification phenomenon and the glass transition temperature vs pressure envelope determined experimentally are well described by the proposed theoretical approach.

Analysis of a Polystyrene-Toluene System through "Dynamic" Sorption Tests: Glass Transitions and Retrograde Vitrification.

Exposing a glassy polymer to a fluid phase (in gaseous or liquid state) containing a low molecular weight compound results in the sorption of the latter within the polymer, inducing, among other effects, the plasticization of the material which also promotes a change in the glass transition temperature. The amount of sorbed penetrant is often related in a complex fashion to the temperature and pressure of the fluid, thus determining that the locus of glass transition, when represented in pressure-temperature coordinates, may display as well rather complex patterns. This is an issue of particular importance in several applications of glassy polymers. In particular, we investigated the behavior of polystyrene in contact with toluene vapor by performing several modes of dynamic sorption experiments, in which the rate of change of the temperature of the system and/or of the pressure of the vapor phase are controlled with high accuracy, with the aim of creating a map of rubbery and glassy states of the polymer as a function of temperature and pressure of the toluene vapor. Isothermal tests were performed by changing the pressure at a controlled rate, isobaric tests were performed by changing the temperature at a controlled rate, and isoactivity tests were performed by concurrently changing, in a proper way, both temperature and pressure. A relevant feature resulting from these experiments is the presence of a discontinuity in the slope of the mass of toluene sorbed within polystyrene reported as a function of temperature and/or pressure. This discontinuity has been interpreted as the indication of the occurrence of a glass transition. The elaboration of the experimental results allowed identification of the pressure/temperature conditions at which rubbery or glassy states of the polymer mixture are established. Quite interestingly, the system displays the so- called "retrograde vitrification" phenomenon, which consists of the occurrence of a rubbery-to-glassy state transition as the temperature increases at a fixed pressure. The whole set of results has been successfully interpreted on the basis of thermodynamics of II order transitions accounting for the fact that experimental evidence of such transitions is significantly affected by the kinetics of polymer relaxation.

Local Structure and Dynamics of Water Absorbed in Poly(ether imide): A Hydrogen Bonding Anatomy.

Hydrogen bonding (HB) interactions play a major role in determining the behavior of macromolecular systems absorbing water. In fact, functional and structural properties of polymer-water mixtures are affected by the amount and type of these interactions. This contribution aims at a molecular level understanding of the interactional scenario for the technologically relevant case of the poly(ether imide)-water system. The problem has been tackled by combining different experimental and theoretical approaches which, taken together, provide a comprehensive physical picture. Relevant experimental data were gathered by in situ FTIR spectroscopy, while molecular dynamics (MD) and statistical thermodynamics approaches were used as modeling theoretical tools. It was found that, among the possible configurations, some are strongly prevailing. In particular, water molecules preferentially establish water bridges with two carbonyl groups of the same PEI repeating unit. Water self-interactions were also detected, giving rise to a "second shell" species in the prevalent form of dimers. The population of the different water species was evaluated spectroscopically, and a remarkable agreement with theoretical predictions was found.

Depth profiles in confocal optical microscopy: a simulation approach based on the second Rayleigh-Sommerfeld diffraction integral.

A method is presented for recovering the intensity depth profile, by confocal optical microscopy, in transparent and amorphous samples with low scattering. The response function of a confocal Raman microscope has been determined by using the second Rayleigh-Sommerfeld diffraction integral and scalar wave optics within paraxial approximation, taking into account the refractive index mismatch between the sample and the medium surrounding the objective lens. An iterative multi-fitting-scheme, based on the conjugate gradient method and Brent algorithm, allowed to fit several depth profile curves simultaneously and retrieve the beam waist, the signal amplitude and the position of the sample surface. The reliability and accuracy of the theoretical procedure has been investigated through comparison with experimental measurements of the Raman depth profiles for different pinhole diameters. The model is shown to provide accurate description of the effect of the mismatch of the refractive index and of the dependence of the Raman signal on the depth with discrepancies lower than 3%. This procedure constitutes a first step towards the development of a manageable theoretical framework, amenable to a relatively simple numerical implementation, for the solution of the 'inverse' problem of finding the correct reconstruction of unknown profiles of chemical species within the sample, starting from experimental information gathered from micro-Raman depth profiling.

Raman Line Imaging of Poly(ε-caprolactone)/Carbon Dioxide Solutions at High Pressures: A Combined Experimental and Computational Study for Interpreting Intermolecular Interactions and Free-Volume Effects.

In the present study, a Raman line-imaging setup was employed to monitor in situ the CO2 sorption at elevated pressures (from 0.62 to 7.10 MPa) in molten PCL. The method allowed the quantitative measurement of gas concentration in both the time-resolved and the space-resolved modes. The combined experimental and theoretical approach allowed a molecular level characterization of the system. The dissolved CO2 was found to occupy a volume essentially coincident with its van der Waals volume and the estimated partial molar volume of the probe did not change with pressure. Lewis acid-Lewis base interactions with the PCL carbonyls was confirmed to be the main interaction mechanism. The geometry of the supramolecular complex and the preferential interaction site were controlled more by steric than electronic effects. On the basis of the indications emerging from Raman spectroscopy, an equation of state thermodynamic model for the PCL-CO2 system, based upon a compressible lattice fluid theory endowed with specific interactions, has been tailored to account for the interaction types detected spectroscopically. The predictions of the thermodynamic model in terms of molar volume of solution have been compared with available volumetric measurements while predictions for CO2 partial molar volume have been compared with the values estimated on the basis of Raman spectroscopy.