Matteo Minelli

Comparing the effect of different atmospheric pressure non-equilibrium plasma sources on PLA oxygen permeability

Plasma technology is widely adopted for polymer surface modification. In this work polylactide (PLA) samples have been exposed to the plasma region generated by three different plasma sources operating at atmospheric pressure: a floating electrode dielectric barrier discharge (FE-DBD), a novel linear corona discharge and a DBD roller. The sources have been supplied with a high voltage generator capable of producing pulses with a rise rate in the order of several kV/ns in order to obtain diffuse plasma and avoid local damage to the membrane; air and argon have been used as working gases. Pure oxygen permeation tests in PLA films have been carried out by means of a closed-volume manometric apparatus working at 35°C with a pressure difference of pure O2 of about 1 bar applied across the membrane. Tests have been performed shortly after the plasma treatment and also replicated at different times in order to investigate the durability of surface modification. The effects of voltage, pulse repetition frequency (PRF) and exposure time on the membrane surface characteristics and barrier property have been studied.

Gas Transport in Glassy Polymers: Prediction of Diffusional Time Lag

The transport of gases in glassy polymeric membranes has been analyzed by means of a fundamental approach based on the nonequilibrium thermodynamic model for glassy polymers (NET-GP) that considers the penetrant chemical potential gradient as the actual driving force of the diffusional process. The diffusivity of a penetrant is thus described as the product of a purely kinetic quantity, the penetrant mobility, and a thermodynamic factor, accounting for the chemical potential dependence on its concentration in the polymer. The NET-GP approach, and the nonequilibrium lattice fluid (NELF) model in particular, describes the thermodynamic behavior of penetrant/polymer mixtures in the glassy state, at each pressure or composition. Moreover, the mobility is considered to follow a simple exponential dependence on penetrant concentration, as typically observed experimentally, using only two adjustable parameters, the infinite dilution penetrant mobility L10 and the plasticization factor β, both determined from the analysis of the dependence of steady state permeability on upstream pressure. The available literature data of diffusional time lag as a function of penetrant upstream pressure has been reviewed and compared with model predictions, obtained after the values of the two model parameters (L10 and β), have been conveniently determined from steady state permeability data. The model is shown to be able to describe very accurately the experimental time lag behaviors for all penetrant/polymer pairs inspected, including those presenting an increasing permeability with increasing upstream pressure. The model is thus more appropriate than the one based on Dual Mode Sorption, which usually provides an unsatisfactory description of time lag and required an ad hoc modification.

Thermodynamic Modeling of Gas Transport in Glassy Polymeric Membranes

Solubility and permeability of gases in glassy polymers have been considered with the aim of illustrating the applicability of thermodynamically-based models for their description and prediction. The solubility isotherms are described by using the nonequilibrium lattice fluid (NELF) (model, already known to be appropriate for nonequilibrium glassy polymers, while the permeability isotherms are described through a general transport model in which diffusivity is the product of a purely kinetic factor, the mobility coefficient, and a thermodynamic factor. The latter is calculated from the NELF model and mobility is considered concentration-dependent through an exponential relationship containing two parameters only. The models are tested explicitly considering solubility and permeability data of various penetrants in three glassy polymers, PSf, PPh and 6FDA-6FpDA, selected as the reference for different behaviors. It is shown that the models are able to calculate the different behaviors observed, and in particular the permeability dependence on upstream pressure, both when it is decreasing as well as when it is increasing, with no need to invoke the onset of additional plasticization phenomena. The correlations found between polymer and penetrant properties with the two parameters of the mobility coefficient also lead to the predictive ability of the transport model.

Water sorption in microfibrillated cellulose (MFC): The effect of temperature and pretreatment

Water sorption behavior of two different microfibrillated cellulose (MFC) films, produced by delamination of cellulose pulp after different pretreatment methods, is examined at various temperatures (16-65°C) and up to 70% RH. The effect of drying temperature of MFC films on the water uptake is also investigated. The obtained solubility isotherms showed the typical downward curvature at moderate RH, while no upturn is observed at higher RH; the uptakes are in line with characteristic values for cellulose fibers. Enzymatically pretreated MFC dispersion showed lower solubility than carboxymethylated MFC, likely due to the different material structure, which results from the different preparation methods The experimental results are analyzed by Park and GAB models, which proved suitable to describe the observed behaviors. Interestingly, while no significant thermal effect is detected on water solubility above 35°C, the uptake at 16 and 25°C, at a given RH, is substantially lower than that at higher temperature, indicating that, in such range, sorption process is endothermic. Such unusual behavior for a cellulose-based system seems to be related mainly to the structural characteristics of MFC films, and to relaxation phenomena taking place upon water sorption. The diffusion kinetics, indeed, showed a clear Fickian behavior at low temperature and RH, whereas a secondary process seems to occur at high temperature and higher RH, leading to anomalous diffusion behaviors.

The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen

This paper presents a study of the effect of moisture on the gas permeability of polyvinyl alcohol (PVOH) and PVOH–kaolin dispersion barrier coatings. The oxygen permeability was measured at different humidity levels, and the material properties were characterized under the same conditions: polymer crystallinity, kaolin concentration, and kaolin orientation were all evaluated. The experimental results revealed that the water plasticizes the PVOH material of the coatings, and the presence of kaolin filler is unable to affect such behavior significantly. The PVOH crystallinity was affected drastically by the humidity, as water melts polymer crystallites, which is a reversible process under removal of water. The permeability data were analyzed using a thermodynamic-based model able to account for the water effect on both the solubility of the gas and the diffusivity coefficients in the polymer and composite. The results showed good agreement between the model’s predictions and the experimental data in terms of the overall permeability of the material.

CO2 induced plasticization in glassy polymeric membranes for gas separation

In gas separation membrane processes, CO2 may induce the plasticization of glassy polymer, lowering its the mechanical rigidity and reducing the glass transition, with a loss of separation performances. Such mechanism is often associated to gas permeability behavior in glassy membranes vs. upstream p, and increasing trends are considered as the footprint of the plasticization onset. However, there is no clear correlation between gas permeability and the effects of CO2 on mechanical behavior. The CO2 induced plasticization in glassy membranes is investigated by direct DMA analysis of polymers saturated at different CO2 pressures. Matrimid polyimide is considered, as it shows a non-monotonous CO2 permeability behavior, and compared to PS (decreasing behavior) and PMMA (increasing).CO2 lowed the elastic modulus of all materials investigated, while the relaxation dynamics revealed a strong enhancement of tan δ, even in absence of a second order transition. The same qualitative behaviors are observed for all glassy systems investigated, and in Matrimid, no apparent change is identified around the pressure value corresponding to the minimum in CO2 permeability, excluding the presence of a new phenomenon onset. Results suggest that increasing permeability behaviors and non-monotonous trends, are not directly related to softening effect induced by CO2 in the polymer matrix, and such features have to be ascribed to the combination of solubility and diffusivity coefficients.In gas separation membrane processes, CO2 may induce the plasticization of glassy polymer, lowering its the mechanical rigidity and reducing the glass transition, with a loss of separation performances. Such mechanism is often associated to gas permeability behavior in glassy membranes vs. upstream p, and increasing trends are considered as the footprint of the plasticization onset. However, there is no clear correlation between gas permeability and the effects of CO2 on mechanical behavior. The CO2 induced plasticization in glassy membranes is investigated by direct DMA analysis of polymers saturated at different CO2 pressures. Matrimid polyimide is considered, as it shows a non-monotonous CO2 permeability behavior, and compared to PS (decreasing behavior) and PMMA (increasing).CO2 lowed the elastic modulus of all materials investigated, while the relaxation dynamics revealed a strong enhancement of tan δ, even in absence of a second order transition. The same qualitative behaviors are observed for all g...

Structure and sieving mechanism of high selective graphene-based membranes

Graphene oxide was used as charge able to confer high selectivity to the final product. A self-assembling technique, namely layer-by-layer has been developed to stratify graphene-based coating on polymeric films; this coating is composed by nanolayers of graphene oxide alternated with polymers, bonded each other by electrostatic forces. Permeability measurement on layered Matrimid®, a commercial polyimide, showed incredibly high selectivity values to small particle mixtures, as O2, CO2, He and H2. Through simple post-treatments the selective performance was also improved, as demonstration of potentiality of the well-ordered bi-dimensional system: improvement on the coating would make this material one of the viable solution for industrial separations, e.g. hydrogen purification in sustainable energy production. A further investigation on similar structures obtained by other strategies shall demonstrate the peculiar mechanism occurring in this material for high selective performance.

Predictive calculations of gas solubility and permeability in glassy polymeric membranes: An overview

The possibility to evaluate in a predictive way the relevant transport properties of low molecular weight species, both gases and vapors, in glassy polymeric membranes is inspected in detail, with particular attention to the methods recently developed based on solid thermodynamic basis. The solubility of pure and mixed gases, diffusivity and permeability of single gases in polymer glasses are examined, considering in particular poly(2,6-dimethyl-1,4-phenylene oxide) as a relevant test case. The procedure clearly indicates what are the relevant physical properties of the polymer matrix and of the penetrants required by the calculations, which can be obtained experimentally through independent measurements. For gas and vapor solubility, the comparison with direct experimental data for mixed gases points out also the ability to account for the significant variations that solubility-selectivity experiences upon variations of pressure and/or feed composition. For gas and vapor permeability, the comparison with direct experimental data shows the possibility to account for the various different trends observed experimentally as penetrant pressure is increased, including the so-called plasticization behavior. The procedure followed for permeability calculations leads also to clear correlations between permeability and physical properties of both polymer and penetrant, based on which pure predictive calculations are reliably made.

Probing effect of solvent concentration on glass transition and sub-Tg structural relaxation in polymer solvent mixtures: The case of polystyrene-toluene system

A novel experimental method for the analysis of volume relaxation induced by solvents in glassy polymers is presented. A gravimetric technique is used to evaluate the isothermal solvent mass uptake at controlled increasing/decreasing solvent pressure at constant rate. Fundamental properties of the solvent/polymer system can be obtained directly, and models can be applied, combining both nonequilibrium thermodynamics and mechanics of volume relaxation contribution. The fundamental case of polystyrene and toluene mixtures are thus accounted for, and various experimental conditions have been explored, varying the temperature, and spanning over different pressure increase/decrease rates. The results obtained allowed to evaluate the isothermal second order transition induced by solvent sorption, as well as the determination of the effect of the pressure rate. Therefore, this work proposes a new standard for the characterization and the understanding of the relaxational behavior of glassy polymers.

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps.