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

doi:10.1007/s11705-017-1615-5

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (3) : 405-413 https://doi.org/10.1007/s11705-017-1615-5

RESEARCH ARTICLE

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

Matteo Minelli, Maria Grazia De Angelis, Giulio C. Sarti(

)

Department of Civil, Chemical, Environmental and Materials Engineering, Alma Mater Studiorum-University of Bologna, Bologna 28-40131, Italy

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Abstract

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.

Keywords solubility permeability glassy polymers NELF model diffusion

Corresponding Author(s): Giulio C. Sarti

Just Accepted Date: 28 December 2016 Online First Date: 13 February 2017 Issue Date: 23 August 2017

Cite this article:

Matteo Minelli,Maria Grazia De Angelis,Giulio C. Sarti. Predictive calculations of gas solubility and permeability in glassy polymeric membranes: An overview[J]. Front. Chem. Sci. Eng., 2017, 11(3): 405-413.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1615-5
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I3/405

Tab.1 Characteristic parameters of the Sanchez Lacombe EoS for the penetrants and polymers systems considered in this work

Tab.2 Binary parameters for the PPO+ gas systems: Binary interaction parameter of the Sanchez Lacombe EoS,k_ij, nonequilibrium swelling coefficient k_sw used by the NELF model, and infinite dilution mobility coefficient and plasticization factor, L₀ and β, of the transport model

Fig.1 CO₂ and CH₄ solubility in glassy PPO at 35 °C: Experimental data after Story and Koros [71], Toi et al. [72] and Hu et al. [73], lines are NELF model calculation curves [68]

Fig.2 Solubility of CO₂ and CH₄ gaseous mixtures in glassy PPO at 35 °C: experimental data after Story and Koros [71], together with NELF model curves [68]

Fig.3 Solubility selectivity for the CO₂/CH₄ separation evaluated in real mixtures relative to that in ideal conditions (pure gases) in glassy PPO at 35 °C: experimental data after Story and Koros [71], together with NELF model curves

Fig.4 CO₂ permeability in glassy PPO at 35 °C: Experimental data after Toi et al. [72], together with transport model curve [48]; the inset illustrates the thermodynamic factor (from NELF model), the mobility coefficientL and the diffusivity D as function of penetrant concentration in the polymer

Fig.5 Light gases permeability in glassy PPO at 35 °C: Experimental data after Toi et al. [72] and Ghosal and Chern [75], together with transport model curve

Fig.6 CO₂ permeability in glassy PPO at 35 °C: Prediction of the “plasticization” point. In the plot, experimental data after Toi et al. [72] are reported together with transport model curve

Fig.7 Parity plot of experimental gas permeability data in various glassy polymers 35 °C with predictions provided by the transport model [81]

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