Diffusion of small molecules in glassy polymers

Pönitsch, M.; Gotthardt, P.; Grüger, A.; Brion, H. G.; Kirchheim, R.

doi:10.1002/(sici)1099-0488(19971115)35:15<2397::aid-polb2>3.0.co;2-r

Cited by 25 publications

(12 citation statements)

References 6 publications

(19 reference statements)

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“…Only the u n -distribution leads to the dependence of diffusion coefficient on gas concentration in polymer. 49,53 This dependence is not sensitive to the form of E nm -distribution. 53 Therefore, all transition states can be taken as similar (the value of E nm is independent of either n, or m).…”

Section: Desorption Of Gasesmentioning

confidence: 87%

“…4 The dependence of diffusion coefficient on gas concentration in polymer originates from the energy distribution of the sorption sites. 49 Actually, as the gas concentration increases, the sites of higher energy are populated which causes a decrease in the mean activation energy of diffusion and thereby an increase in the diffusion coefficient, D. The effect of temperature is due to purely a decrease in r =k B T with increasing T. As a consequence, the dependence of D on gas concentration manifests itself in the kinetics of gas desorption shown in Figures 3 and 4 (Supporting Information, Figures S2-S5).…”

Section: Desorption Of Gasesmentioning

confidence: 99%

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Sorption of light gases in glassy poly(ethyl methacrylate)

Большаков

Syutkin

Vyazovkin

et al. 2017

J Polym Sci B Polym Phys

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Although gas sorption in glassy polymers is a well‐studied phenomenon, no general microscopical model is developed which is able to describe the gas sorption in a wide temperature range using only characteristics of polymer and gas molecule. In this work, sorption isotherms and desorption kinetics of O2, Ar, and N2 for glassy poly(ethyl methacrylate) have been measured in the temperature range from 160 to 308 K. To describe both the phenomena, the model is developed which postulates that, in the frozen structure of glassy polymer, any cavities between macromolecules are the sorption sites for small molecules. The cavities of small size can expand elastically to accommodate a gas molecule. The sorption sites are considered to be the potential wells and their depths are distributed according to Gaussian law. The concentration of sorption sites, their mean depth and depths dispersion, and the frequency of molecules oscillations in the sorption sites are the only parameters which determine both the gas transport and sorption. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 288–296

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Section: Desorption Of Gasesmentioning

confidence: 87%

Section: Desorption Of Gasesmentioning

confidence: 99%

Sorption of light gases in glassy poly(ethyl methacrylate)

Большаков

Syutkin

Vyazovkin

et al. 2017

J Polym Sci B Polym Phys

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“…It is also well understood that segmental molecular motions, either along the backbone or localized to side groups, dramatically affect the kinetics of small‐molecule transport through polymeric materials 70, 71. Several authors have argued that these motions produce a gating effect that regulates gas or small‐molecule transport through the interchain regions of amorphous polymers 72–75. This effect should be of consequence in deep UV lithography, in which a photochemically generated acidic proton (H + ) must diffuse through a photoresist film, accompanied by some sort of counterion, to induce multiple chemical reactions.…”

Section: Discussionmentioning

confidence: 99%

Dynamics of thin polymer films: Recent insights from incoherent neutron scattering

Soles

Douglas

2004

J Polym Sci B Polym Phys

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Incoherent neutron scattering is presented as a powerful tool for interpreting changes in molecular dynamics as a function of film thickness for a range of polymers. Motions on approximately nanosecond and faster timescales are quantified in terms of a mean-square atomic displacement (͗u 2 ͘) from the Debye-Waller factor. Thin-film confinement generally leads to a reduction of ͗u 2 ͘ in comparison with the bulk material, and this effect becomes especially pronounced when the film thickness approaches the unperturbed dimensions of the macromolecule. Generally, there is a suppression (never an enhancement) of ͗u 2 ͘ at temperatures T above the bulk calorimetric glass-transition temperature (T g ). Below T g , the reduction in the magnitude of ͗u 2 ͘ depends on the polymer and the length scales being probed. Polymers with extensive segmental or local mobility in the glass are particularly susceptible to reductions of ͗u 2 ͘ with confinement, especially at the Q vectors probing these longer length scales, whereas materials lacking these sub-T g motions are relatively insensitive. Moreover, a reduced ͗u 2 ͘ value correlates with reduced mobility at long time and spatial scales, as measured by diffusion in these thin polymer films. Finally, this reduced thin-film mobility is not reliably predicted by thermodynamic assessments of an apparent T g , as measured by discontinuities or kinks in the T dependence of the thermal expansion, specific volume, index of refraction, specific heat, and so forth. These measurements illustrate that ͗u 2 ͘ is a powerful and predictive tool for understanding dynamic changes in thin polymer films.

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“…Zhou and Stern extended this model by considering the effect of solvent plasticization 5. Recently, a novel model has been proposed6 in terms of the idea that small molecules in a glassy polymer occupy sites with a distribution of free energies of dissolution, and their diffusivity depends on concentration and temperature in the same way. Although these models provide useful approaches for correlating experimental results with theories, the presence of adjustable parameters that are determined by sorption or diffusion measurements makes application difficult.…”

Section: Introductionmentioning

confidence: 99%

Solvent diffusion in amorphous glassy polymers

Wang

Yamaguchi

Nakao

2000

J. Polym. Sci. B Polym. Phys.

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In this article, a mathematical model is proposed for predicting solvent self‐diffusion coefficients in amorphous glassy polymers based on free volume theory. The basis of this new model involves consideration of the plasticization effects induced by small molecular solvents to correctly estimate the hole‐free volume variation above and below the glass‐transition temperature. Solvent mutual‐diffusion coefficients are calculated using free volume parameters determined as in the original theory. Only one parameter, which can be predicted by thermodynamic theory, is introduced to express the plasticization effect. Thus, this model permits the prediction of diffusion coefficients without adjustable parameters. Comparison of the values calculated by this new model with the present experimental data, including benzene, toluene, ethyl benzene, methyl acetate, and methyl ethyl ketone (MEK) in polystyrene (PS) and poly(methyl methacrylate) (PMMA), has been performed, and the results show good agreement between the predicted and measured values. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 846–856, 2000

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Diffusion of small molecules in glassy polymers

Cited by 25 publications

References 6 publications

Sorption of light gases in glassy poly(ethyl methacrylate)

Sorption of light gases in glassy poly(ethyl methacrylate)

Dynamics of thin polymer films: Recent insights from incoherent neutron scattering

Solvent diffusion in amorphous glassy polymers

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