Application of non-equilibrium thermodynamics and computer aided analysis to the estimation of diffusion coefficients in polymer solutions: The solvent evaporation method☆

Verros, George D.

doi:10.1016/j.memsci.2008.10.027

Cited by 11 publications

(13 citation statements)

References 135 publications

(339 reference statements)

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“…To validate models to predict multicomponent mass transport, measurement data is still a necessity. Often integral measurement data such as mass loss during drying of polymer films are used to validate diffusion models . However, this information does not allow differentiating between the different solvents and is much more suitable for binary polymer solutions than in the ternary case.…”

Section: Introductionmentioning

confidence: 99%

“…Often integral measurement data such as mass loss during drying of polymer films are used to validate diffusion models. 8,25,26 However, this informa-tion does not allow differentiating between the different solvents and is much more suitable for binary polymer solutions than in the ternary case. Studies with FTIR-analysis 27,28 of drying experiments for example offer this information, but local data within the samples, that is, the concentration profiles, remain inaccessible.…”

Section: Introductionmentioning

confidence: 99%

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Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Siebel

Scharfer

Schabel

2016

J of Applied Polymer Sci

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Multicomponent diffusion of solvents in polymeric systems is not completely understood, despite many scientific contributions to the topic. Literature scarcely offers measurement data on diffusion for model validation in such systems. In this work, the ternary systems consisting of poly(vinyl acetate) and the solvents toluene and methanol was investigated experimentally and numerically. By means of inverse micro Raman spectroscopy (IMRS) concentration gradients in drying thin films have been measured. Initial composition of the samples has been varied systematically in order to detect mutual influence of the solvents' diffusive behavior. It was shown that the mobility of the different species is increased in the presence of other solvents as predicted by theory. This experimental data is provided for model validation. A new expression to calculate the diffusion coefficients in ternary mixtures is proposed which only requires binary data. This expression is tested by means of a model-based simulation to predict the drying of ternary polymer solutions in terms of concentration profiles and residual solvent content. The results are in very good agreement with the experiments. Cross terms diffusion coefficients and thermodynamic factors were not found to be necessary for a satisfying prediction.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Siebel

Scharfer

Schabel

2016

J of Applied Polymer Sci

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“…[50][51][52] The aim of this work is to reduce the complicated physical framework for case-II diffusion to a close-to-equilibrium state where the well-established framework of solvent diffusion in the rubbery state could be applied. On the other hand, work on the application of irreversible thermodynamics close to equilibrium to the membrane formation by solvent evaporation has appeared in the literature.…”

Section: Onsager Reciprocal Relations (Orr)mentioning

confidence: 99%

“…[51,58] An energy balance at the moving interface was formulated (see Table 2), equating the heat conduction to the polymer solution with forced convection heat transfer, radiant heat transfer from the ambient air, and latent heat loss due to toluene evaporation. More specifically, appropriate mass and energy balances at the moving interface were written in terms of the heat and mass transfer coefficients.…”

Section: Modelling Solvent Evaporation From Toluene-poly(methyl Methamentioning

confidence: 99%

“…On the other hand, work on the application of irreversible thermodynamics close to equilibrium to the membrane formation by solvent evaporation has appeared in the literature. [50][51][52] The aim of this work is to reduce the complicated physical framework for case-II diffusion to a close-to-equilibrium state where the well-established framework of solvent diffusion in the rubbery state could be applied. This is achieved in this work by using appropriate variable transformations.…”

Section: Onsager Reciprocal Relations (Orr)mentioning

confidence: 99%

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Application of irreversible thermodynamics to the solvent diffusion in an amorphous glassy polymer: A comprehensive model for drying of toluene‐poly(methyl methacrylate) coatings

Verros

2015

Can J Chem Eng

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In this work a comprehensive framework for modelling solvent-polymer mutual diffusion coefficient in the glassy state is proposed. This framework is based on irreversible thermodynamics. In particular, an appropriate transformation is used to show that case-II diffusion appearing in the glassy state could be reduced to a close-to-equilibrium rubbery state where typical equations relating the solvent-polymer mutual diffusion coefficient with chemical potential and the solvent self-diffusion coefficient are available. Moreover, this theory is applied to solvent evaporation from a toluenepoly(methyl methacrylate) film. The toluene evaporation process is modelled as a coupled heat and mass problem with a moving boundary. Model predictions were found to be in satisfactory agreement with available experimental data. It is believed that this work could be used to further study solvent diffusion in the glassy polymer state.

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Modeling of diffusion‐controlled reactions in free radical solution and bulk polymerization: Model validation by DSC experiments

Achilias¹,

Verros²

2010

J of Applied Polymer Sci

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In this work, a detailed experimental study of diffusion-controlled reactions in free radical polymerization by using differential scanning calorimetry (DSC) was carried out. The systems studied include the methyl methacrylate bulk polymerization as well as the solution and the bulk polymerization of vinyl acetate at a wide range of experimental conditions including initial initiator concentration, reaction temperature, and type and amount of solvent. The conversion data obtained by DSC was successfully simulated by using a mathematical model based on sound principles such as the free volume theory. The estimated parameters, by fitting predictions of this model to conversion data obtained by DSC were found to be in close agreement with the reported parameters in the literature, thus validating both the experimental and theoretical methods used in this work.

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Application of non-equilibrium thermodynamics and computer aided analysis to the estimation of diffusion coefficients in polymer solutions: The solvent evaporation method☆

Cited by 11 publications

References 135 publications

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Prediction of diffusion in a ternary solvent–solvent–polymer blend by means of binary diffusion data: Comparison of experimental data and simulative results

Application of irreversible thermodynamics to the solvent diffusion in an amorphous glassy polymer: A comprehensive model for drying of toluene‐poly(methyl methacrylate) coatings

Modeling of diffusion‐controlled reactions in free radical solution and bulk polymerization: Model validation by DSC experiments

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