Maria Grazia De Angelis

Solubility of Gases and Liquids in Glassy Polymers

This review discusses a macroscopic thermodynamic procedure to calculate the solubility of gases, vapors, and liquids in glassy polymers that is based on the general procedure provided by the nonequilibrium thermodynamics for glassy polymers (NET-GP) method. Several examples are presented using various nonequilibrium (NE) models including lattice fluid (NELF), statistical associating fluid theory (NE-SAFT), and perturbed hard sphere chain (NE-PHSC). Particular applications illustrate the calculation of infinite-dilution solubility coefficients in different glassy polymers and the prediction of solubility isotherms for different gases and vapors in pure polymers as well as in polymer blends. The determination of model parameters is discussed, and the predictive abilities of the models are illustrated. Attention is also given to the solubility of gas mixtures and solubility isotherms in nanocomposite mixed matrices. The fractional free volume determined from solubility data can be used to correlate solute diffusivities in mixed matrices.

Permeability and Selectivity of PPO/Graphene Composites as Mixed Matrix Membranes for CO2 Capture and Gas Separation

We fabricated novel composite (mixed matrix) membranes based on a permeable glassy polymer, Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), and variable loadings of few-layer graphene, to test their potential in gas separation and CO2 capture applications. The permeability, selectivity and diffusivity of different gases as a function of graphene loading, from 0.3 to 15 wt %, was measured at 35 and 65 °C. Samples with small loadings of graphene show a higher permeability and He/CO2 selectivity than pure PPO, due to a favorable effect of the nanofillers on the polymer morphology. Higher amounts of graphene lower the permeability of the polymer, due to the prevailing effect of increased tortuosity of the gas molecules in the membrane. Graphene also allows dramatically reducing the increase of permeability with temperature, acting as a “stabilizer” for the polymer matrix. Such effect reduces the temperature-induced loss of size-selectivity for He/N2 and CO2/N2, and enhances the temperature-induced increase of selectivity for He/CO2. The study confirms that, as observed in the case of other graphene-based mixed matrix glassy membranes, the optimal concentration of graphene in the polymer is below 1 wt %. Below such threshold, the morphology of the nanoscopic filler added in solution affects positively the glassy chains packing, enhancing permeability and selectivity, and improving the selectivity of the membrane at increasing temperatures. These results suggest that small additions of graphene to polymers can enhance their permselectivity and stabilize their properties.

Mass Transport in Nanocomposite Materials for Membrane Separations

The vapor transport properties of nanocomposite materials obtained with different techniques and based on a high free volume glassy polymer suitable for membrane separations, poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP), have been determined and modeled. The simple mixing in solution of hydrophobic fumed silica nanoparticles with PTMSP leads to mixed matrix membranes, which show higher free volume and higher values of diffusivity and permeability than the pure polymeric material. If a sol‐gel route is followed, with PTMSP and Tetraethoxysylane (TEOS) as precursor of the silica phase, one obtains hybrid matrices characterized by lower vapor diffusion and sorption values with respect to the pure polymer. Although the trends observed are very regular functions of the silica content in the composite, none of the behavior observed obeys traditional models for composites permeability, such as the Maxwell’s one. Both types of behaviors were modeled considering the variation of polymer fractional free volume induced by the inorganic phase: in the mixed matrices the poor interactions between silica and polymer chains favor the formation of nanovoids at the interface, increasing the free volume and the vapor diffusivity, while in the more interconnected hybrid matrices the inorganic domains act as constraints, reducing the volume occupied by the polymeric phase, which is naturally endowed with a very high excess free volume.

Effect of relative humidity on the gas transport properties of zeolite A/PTMSP mixed matrix membranes

Increasing the knowledge of the influence of water vapor in new mixed matrix membranes (MMMs) could favor the integration of novel membrane materials in the recovery of CO2 from wet industrial streams. In this work, the water vapor effect on the N2, CH4 and CO2 permeability through MMMs comprised of 20 wt% hydrophilic zeolite 4A in hydrophobic PTMSP polymer were investigated in the relative humidity range 0–75%. While in the pure PTMSP membranes, the permeability of all gases decreases with water vapor activity, with almost unchanged CO2/N2 and CO2/CH4 selectivities, in zeolite A/PTMSP MMMs, the CO2 permeability increases with increasing water content in the system up to 50% R.H., resulting in an increase in CO2/N2 and CO2/CH4 selectivities with respect to pure PTMSP. Gas sorption was studied so that the effect the residual humidity in the zeolite 4A has on the sorption of the different gases helped explaining the permeability observations. The sorption and humid permeation behavior were evaluated by a simple model equation based on the NELF theory, taking into account the multicomponent gas sorption and diffusion in the presence of humidity, as well as the counteracting effects of the hydrophobic PTMSP and hydrophilic zeolite A in a very accurate way.

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.

Modeling VOC Sorption and Transport in Glassy Polymeric Membranes

In this work we evaluated the sorption, diffusion and permeation of a series of volatile organic compounds (VOCs) (acetone, n‐butane, n‐pentane, n‐hexane, ethanol, methanol, chloroform and toluene) into glassy polymers of increasing fractional free volume (FFV): Polycarbonate (PC), Amorphous Teflon AF1600 and AF2400, poly‐trimethylsilyl norbornene (PTMSN) and poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP). Based on some experimental data of sorption and diffusion, and on theoretical and empirical models for the solubility and diffusion coefficients, the permeability for vapor/N2 mixtures was evaluated. These parameters are useful for the membrane separation processes and for other applications such as chemical sensors. The ideal separation factors of glassy polymeric membranes versus mixtures of VOCs and N2 were estimated at various pressures and compositions and at 25° C. The selectivity vs. permeability maps for the mixtures considered were plotted, showing that some of these materials show potentially the same selective ability of rubbery polymeric films. In particular it is shown that, the higher the FFV, the better the vapor/gas selectivity.In this work we evaluated the sorption, diffusion and permeation of a series of volatile organic compounds (VOCs) (acetone, n‐butane, n‐pentane, n‐hexane, ethanol, methanol, chloroform and toluene) into glassy polymers of increasing fractional free volume (FFV): Polycarbonate (PC), Amorphous Teflon AF1600 and AF2400, poly‐trimethylsilyl norbornene (PTMSN) and poly[1‐(trimethylsilyl)‐1‐propyne] (PTMSP). Based on some experimental data of sorption and diffusion, and on theoretical and empirical models for the solubility and diffusion coefficients, the permeability for vapor/N2 mixtures was evaluated. These parameters are useful for the membrane separation processes and for other applications such as chemical sensors. The ideal separation factors of glassy polymeric membranes versus mixtures of VOCs and N2 were estimated at various pressures and compositions and at 25° C. The selectivity vs. permeability maps for the mixtures considered were plotted, showing that some of these materials show potentially the ...

Water Transport in Proton Exchange Membranes: Insights from Time-Resolved Infrared Spectroscopy

Water transport in proton exchange membranes (PEMs) is relevant to several advanced technologies, especially fuel cells. The dynamics of changing water conditions can significantly impact the PEM conductivity and fuel cell performance. Accurate water diffusion coefficients in Nafion, the industry standard PEM, have been determined, non-Fickian regimes identified and modeled, and infrared data used to confirm the validity of these models.