Predictive Model for the Solubility of Fluid Mixtures in Glassy Polymers

Minelli, Matteo; Campagnoli, S.; Angelis, Maria Grazia De; Doghieri, Ferruccio; Sarti, Giulio Cesare

doi:10.1021/ma200602d

Cited by 74 publications

(69 citation statements)

References 81 publications

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“…[19,27] That behavior appears to be independent of the total pressure or partial pressure of penetrants and of gaseous mixture composition. When the polymer contains similar molar concentrations of both penetrants, the extent of solubility depression is practically the same for 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 13 both penetrants.…”

Section: Pure Gas Solubility Isothermsmentioning

confidence: 98%

“…The experimental data collected in part I and part II of this work will later be used, in part III of this work, to test, validate and compare the performance of two models for multicomponent solubility in glassy polymeric membranes, namely the Dual Mode model [23][24] and the Nonequilibrium Lattice Fluid (NELF) model. [25][26][27] 1. Experimental…”

Section: Introductionmentioning

confidence: 99%

“…10 the same quantity is reported versus the ratio between the actual CO 2 and methane molar concentrations in the polymer, c(CO 2 )/c(CH 4 ): the higher-than-ideal behavior of the selectivity is observed, in particular, when the molar fraction of CO 2 in the polymer overcomes that of methane, as it was also observed for other polymers, in particular in PPO and in PTMSP with the same gas mixture. [19,27] In PPO, a lower-than-ideal behavior is observed when c(CO 2 ) < 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 25 c(CH 4 ), [19] while in PTMSP the solubility selectivity follows an ideal trend in this range. [19] In particular one can draw the following correlations for PIM-1: …”

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confidence: 99%

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Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Vopička

Angelis

et al. 2014

Journal of Membrane Science

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The individual solubility of CH 4 and CO 2 from binary gas mixtures was measured at 35 °C and up to 35 bar in a polymer of intrinsic microporosity (PIM-1), at different compositions of the gas phase (from 0 to 50 mol% of CO 2 ). The experiments were conducted on a pressure-decay apparatus equipped with a gas chromatograph, allowing a highly flexible measuring procedure. The gas solubility was plotted versus gas phase composition, total pressure, gas fugacity and second gas concentration. The mixed gas solubility of both species, CH 4 and CO 2 , is lower than the pure gas value at the same fugacity, but the reduction of methane solubility due to the presence of CO 2 is generally more significant. Such behavior is due to the fact that CO 2 has normally higher solubility than methane: indeed the depression of the solubility coefficient with respect to the pure gas value is similar for both gases, when reported at the same concentration of the second gas.The real, mixed gas solubility selectivity is in general higher than the ideal value calculated from pure gas behavior. The ratio between real and ideal solubility selectivity increases with CO 2 concentration in the membrane, according to a single mastercurve, reaching a maximum value of 4, and increases also with the ratio between CO 2 and CH 4 concentration in the membrane. In particular, as in the case of other glassy polymers, the real solubility selectivity of CO 2 over CH 4 is higher than the ideal value if c(CO 2 )>c(CH 4 ), and it is lower than the ideal value if the opposite condition holds true. Such behavior occurs because the competition for sorption is normally less effective on the more abundant penetrant in the polymer. A selectivity-solubility performance plot can be drawn for this system.

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Section: Pure Gas Solubility Isothermsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Vopička

Angelis

et al. 2014

Journal of Membrane Science

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“…Finally, the thermodynamic model for solubility and permeability is suitable for any kind of penetrant/polymer couple, and it has already been employed for gases, mixtures, vapors, and even liquids …”

Section: Resultsmentioning

confidence: 99%

Modeling of oxygen permeation through filled polymeric layers for barrier coatings

Nyflött

Petkova-Olsson

Moons

et al. 2017

J of Applied Polymer Sci

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This paper presents an extended model for gas permeation through a filled polymer layer, and it is applied to the case of oxygen permeability through a poly(vinyl alcohol)/kaolin dispersion coating. The model is based on a description of polymer and penetrant properties in a thermodynamically consistent framework. The gradient in chemical potential is considered the driving force for the diffusion of the penetrating gas. The well‐established nonequilibrium lattice fluid (NELF) model for the polymer phase is extended in order to account for the additional features of the polymer/filler system, such as the concentration and aspect ratio of the inorganic filler, which enhance the penetrant tortuosity. The model predicts the behavior of penetrant permeability with respect to polymer crystallinity and filler fraction. The calculated results are compared to experimentally obtained data for oxygen permeability through a dispersion coating layer consisting of poly(vinyl alcohol) (PVOH) and two types of kaolin with different aspect ratios. A good agreement is found in terms of the effects of polymer crystallinity, filler concentration, and filler aspect ratio. The experimental results also indicate a complex interplay between the polymer and the filler as the permeability of two differently surface modified kaolin clays was determined, displaying slight deviations from model predictions. Significant differences were observed in the experimental results between the two fillers investigated, and the one characterized by the smaller aspect ratio affects to a minor extent the oxygen permeability, as illustrated by the model. Furthermore, the lower hydrolysis degree of PVOH gives a reduced barrier performance, as expected. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44834.

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“…The NET-GP approach was used with several EOS to describe sorption of pure gases (Doghieri & Sarti, 1996;Doghieri et al, 2004;Giacinti Baschetti et al, 2001;Giacinti Baschetti et al, 2005), liquids (Sarti & De Angelis, 2012) and mixtures (Minelli, Campagnoli, Angelis, Doghieri, & Sarti, 2011) in glassy polymers. For vapours, application can be found related to water vapour, dichloromethane, methyl acetate, acetone and methanol in Matrimid polyimide (Minelli et al, 2013), where data in both glassy and rubbery states were predicted with the same set of adjustable parameters, obtaining more than satisfactory agreement between the data and the model results, as can be seen in Figure 8.8.…”

Section: Extension To Glassy Systemsmentioning

confidence: 99%