Calculation of the solubility of liquid solutes in glassy polymers

Sarti, Giulio Cesare; Angelis, Maria Grazia De

doi:10.1002/aic.12571

Cited by 35 publications

(16 citation statements)

References 51 publications

(84 reference statements)

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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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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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“…As a result, nonequilibrium theory (NET) was developed to account for the effect in the past decade. , The main spirit of NET is to use the order parameter for the nonequilibrium state, and the glassy phase is described by the free energy from existing EOS models. The calculated result is extremely accurate compared to the experimental data for the gas solubility in glassy polymer, and the Langmuir sorption effect can be adequately represented by these models. − However, values of the pure parameters of a polymer must be determined from experimental P V T data. Furthermore, some experimental data (e.g., volume dilation for polymers during the gas sorption process) are acquired to determine the order parameters.…”

Section: Introductionmentioning

confidence: 88%

Prediction of Gas and Liquid Solubility in Organic Polymers Based on the PR+COSMOSAC Equation of State

Wang

Hsieh

Lin

2018

Ind. Eng. Chem. Res.

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The predictive capability of gas and liquid solubility in organic polymers is examined based on the combination of the PR+COSMOSAC equation of state (EOS) and the COSMO-SAC liquid model through three different excess Gibbs free energy based mixing rules, modified Huron-Vidal (MHV1), Wong-Sandler (WS), and self-consistent mixing rule (SCMR). Using 81 binary systems consisting of 23 gas molecules and 22 polymers (81 data points) with temperatures ranging from 298 to 461 K, it is found that WS and SCMR can provide reasonable prediction accuracy (RMSE(log10 k H) = 0.746 and 1.725, respectively) for the Henry’s law parameter in polymers, while the MHV1 mixing rule results in a much larger error (RMSE (log10 k H) = 3.118) compared to experiment. The WS and SCMR, but not MHV1, provide a converged value of Henry’s law parameter of gas in polymers as the molecular weight of the polymer increases. We further propose a modification to the SCMR (mSCMR) that results in significant improvement in the solubility prediction in polymers (RMSE (log10 k H) = 0.305) and the binary vapor–liquid equilibrium for common molecules. In this new approach, referred to as PRCS/mSCMR/COSMOSAC, all species-dependent parameters are determined from quantum mechanical (QM) calculations, and no adjustable parameters are required for the gas–polymer binary pairs. We believe that this new method may provide useful assistance to the development of polymer membrane-based gas separation processes especially when experimental information is not yet available.

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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%