Sorption and permeation of gases in hyper-cross-linked hybrid poly(POSS-imide) networks: An in silico study

David Brown* (Corresponding Author), Sylvie Neyertz, Michiel J.T. Raaijmakers, Nieck E. Benes

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Networked hybrid materials containing various types of organic imides covalently bonded with polyhedral oligomeric silsesquioxanes (POSS) have recently been developed. One of their possible applications is for gas-separation under extreme conditions of pressure and/or temperature. Experimental results indicate that their permeation properties depend on the specific organic dianhydride precursor used in the synthesis. In this work, atomistic models of 6FDA-based and PMDA-based poly(POSS-imide) crosslinked networks have been used to investigate the sorption, desorption, relaxation and permeation properties of such materials at the molecular level and their dependence on the nature of the imide linker. Results have been compared to available experimental data. A highly-efficient parallelised version of the excluded volume map sampling test particle insertion (EVMS-TPI) method was used to obtain the infinite dilution solubilities of a number of small penetrants (N 2 , O 2 , CH 4 and CO 2 ) in these model networks. Analyses of the Boltzmann-weighted probability densities for the distribution of the insertion energies showed that very reliable estimates of solubilities could be obtained. Extensive molecular dynamics simulations were then performed to obtain the complete model sorption isotherms for CO 2 and CH 4 at 35 °C up to pressures of over 60 bar using an iterative technique which matches the chemical potential of the penetrant in the poly(POSS-imide) phase to that in the corresponding gas phase. The sorption-induced changes in volume, the significant space available to penetrants, the mean insertion energies and their distributions were characterized. Comparisons were not only made between both types of poly(POSS-imide) to characterize the effect of the linker, but also with (hypothetical) uncrosslinked mixtures of the POSS and dianhydride molecules in order to elucidate the effects of crosslinking. Given the known conditioning properties of CO 2 , desorption isotherms were also obtained for this penetrant. These showed significant hysteresis. Prolonged exposure to high concentrations of CO 2 was also found to lead to slow relaxations that have significant effects on the solubility. Permeabilities were obtained for methane and carbon dioxide at 100 °C, 200 °C and 300 °C at a pressure of ~ 2 bar. Differences in permeabilities were largely diffusion dependent.

Original languageEnglish
Pages (from-to)113-128
Number of pages16
JournalJournal of membrane science
Volume577
Early online date28 Jan 2019
DOIs
Publication statusPublished - 1 May 2019

Fingerprint

Imides
penetrants
imides
Permeation
Computer Simulation
sorption
Sorption
Carbon Monoxide
Solubility
Gases
Isotherms
Desorption
insertion
gases
solubility
Pressure
Chemical potential
Hybrid materials
Permeability
permeability

Keywords

  • 6FDA and PMDA poly(POSS-imide) networks
  • Carbon dioxide and methane sorption, diffusion and permeation
  • Molecular dynamics (MD) simulations

Cite this

@article{0710c9138eb34d5d8939411935e84dd2,
title = "Sorption and permeation of gases in hyper-cross-linked hybrid poly(POSS-imide) networks: An in silico study",
abstract = "Networked hybrid materials containing various types of organic imides covalently bonded with polyhedral oligomeric silsesquioxanes (POSS) have recently been developed. One of their possible applications is for gas-separation under extreme conditions of pressure and/or temperature. Experimental results indicate that their permeation properties depend on the specific organic dianhydride precursor used in the synthesis. In this work, atomistic models of 6FDA-based and PMDA-based poly(POSS-imide) crosslinked networks have been used to investigate the sorption, desorption, relaxation and permeation properties of such materials at the molecular level and their dependence on the nature of the imide linker. Results have been compared to available experimental data. A highly-efficient parallelised version of the excluded volume map sampling test particle insertion (EVMS-TPI) method was used to obtain the infinite dilution solubilities of a number of small penetrants (N 2 , O 2 , CH 4 and CO 2 ) in these model networks. Analyses of the Boltzmann-weighted probability densities for the distribution of the insertion energies showed that very reliable estimates of solubilities could be obtained. Extensive molecular dynamics simulations were then performed to obtain the complete model sorption isotherms for CO 2 and CH 4 at 35 °C up to pressures of over 60 bar using an iterative technique which matches the chemical potential of the penetrant in the poly(POSS-imide) phase to that in the corresponding gas phase. The sorption-induced changes in volume, the significant space available to penetrants, the mean insertion energies and their distributions were characterized. Comparisons were not only made between both types of poly(POSS-imide) to characterize the effect of the linker, but also with (hypothetical) uncrosslinked mixtures of the POSS and dianhydride molecules in order to elucidate the effects of crosslinking. Given the known conditioning properties of CO 2 , desorption isotherms were also obtained for this penetrant. These showed significant hysteresis. Prolonged exposure to high concentrations of CO 2 was also found to lead to slow relaxations that have significant effects on the solubility. Permeabilities were obtained for methane and carbon dioxide at 100 °C, 200 °C and 300 °C at a pressure of ~ 2 bar. Differences in permeabilities were largely diffusion dependent.",
keywords = "6FDA and PMDA poly(POSS-imide) networks, Carbon dioxide and methane sorption, diffusion and permeation, Molecular dynamics (MD) simulations",
author = "David Brown and Sylvie Neyertz and Raaijmakers, {Michiel J.T.} and Benes, {Nieck E.}",
year = "2019",
month = "5",
day = "1",
doi = "10.1016/j.memsci.2019.01.039",
language = "English",
volume = "577",
pages = "113--128",
journal = "Journal of membrane science",
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}

Sorption and permeation of gases in hyper-cross-linked hybrid poly(POSS-imide) networks : An in silico study. / Brown, David (Corresponding Author); Neyertz, Sylvie; Raaijmakers, Michiel J.T.; Benes, Nieck E.

In: Journal of membrane science, Vol. 577, 01.05.2019, p. 113-128.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Sorption and permeation of gases in hyper-cross-linked hybrid poly(POSS-imide) networks

T2 - An in silico study

AU - Brown, David

AU - Neyertz, Sylvie

AU - Raaijmakers, Michiel J.T.

AU - Benes, Nieck E.

PY - 2019/5/1

Y1 - 2019/5/1

N2 - Networked hybrid materials containing various types of organic imides covalently bonded with polyhedral oligomeric silsesquioxanes (POSS) have recently been developed. One of their possible applications is for gas-separation under extreme conditions of pressure and/or temperature. Experimental results indicate that their permeation properties depend on the specific organic dianhydride precursor used in the synthesis. In this work, atomistic models of 6FDA-based and PMDA-based poly(POSS-imide) crosslinked networks have been used to investigate the sorption, desorption, relaxation and permeation properties of such materials at the molecular level and their dependence on the nature of the imide linker. Results have been compared to available experimental data. A highly-efficient parallelised version of the excluded volume map sampling test particle insertion (EVMS-TPI) method was used to obtain the infinite dilution solubilities of a number of small penetrants (N 2 , O 2 , CH 4 and CO 2 ) in these model networks. Analyses of the Boltzmann-weighted probability densities for the distribution of the insertion energies showed that very reliable estimates of solubilities could be obtained. Extensive molecular dynamics simulations were then performed to obtain the complete model sorption isotherms for CO 2 and CH 4 at 35 °C up to pressures of over 60 bar using an iterative technique which matches the chemical potential of the penetrant in the poly(POSS-imide) phase to that in the corresponding gas phase. The sorption-induced changes in volume, the significant space available to penetrants, the mean insertion energies and their distributions were characterized. Comparisons were not only made between both types of poly(POSS-imide) to characterize the effect of the linker, but also with (hypothetical) uncrosslinked mixtures of the POSS and dianhydride molecules in order to elucidate the effects of crosslinking. Given the known conditioning properties of CO 2 , desorption isotherms were also obtained for this penetrant. These showed significant hysteresis. Prolonged exposure to high concentrations of CO 2 was also found to lead to slow relaxations that have significant effects on the solubility. Permeabilities were obtained for methane and carbon dioxide at 100 °C, 200 °C and 300 °C at a pressure of ~ 2 bar. Differences in permeabilities were largely diffusion dependent.

AB - Networked hybrid materials containing various types of organic imides covalently bonded with polyhedral oligomeric silsesquioxanes (POSS) have recently been developed. One of their possible applications is for gas-separation under extreme conditions of pressure and/or temperature. Experimental results indicate that their permeation properties depend on the specific organic dianhydride precursor used in the synthesis. In this work, atomistic models of 6FDA-based and PMDA-based poly(POSS-imide) crosslinked networks have been used to investigate the sorption, desorption, relaxation and permeation properties of such materials at the molecular level and their dependence on the nature of the imide linker. Results have been compared to available experimental data. A highly-efficient parallelised version of the excluded volume map sampling test particle insertion (EVMS-TPI) method was used to obtain the infinite dilution solubilities of a number of small penetrants (N 2 , O 2 , CH 4 and CO 2 ) in these model networks. Analyses of the Boltzmann-weighted probability densities for the distribution of the insertion energies showed that very reliable estimates of solubilities could be obtained. Extensive molecular dynamics simulations were then performed to obtain the complete model sorption isotherms for CO 2 and CH 4 at 35 °C up to pressures of over 60 bar using an iterative technique which matches the chemical potential of the penetrant in the poly(POSS-imide) phase to that in the corresponding gas phase. The sorption-induced changes in volume, the significant space available to penetrants, the mean insertion energies and their distributions were characterized. Comparisons were not only made between both types of poly(POSS-imide) to characterize the effect of the linker, but also with (hypothetical) uncrosslinked mixtures of the POSS and dianhydride molecules in order to elucidate the effects of crosslinking. Given the known conditioning properties of CO 2 , desorption isotherms were also obtained for this penetrant. These showed significant hysteresis. Prolonged exposure to high concentrations of CO 2 was also found to lead to slow relaxations that have significant effects on the solubility. Permeabilities were obtained for methane and carbon dioxide at 100 °C, 200 °C and 300 °C at a pressure of ~ 2 bar. Differences in permeabilities were largely diffusion dependent.

KW - 6FDA and PMDA poly(POSS-imide) networks

KW - Carbon dioxide and methane sorption, diffusion and permeation

KW - Molecular dynamics (MD) simulations

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U2 - 10.1016/j.memsci.2019.01.039

DO - 10.1016/j.memsci.2019.01.039

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JO - Journal of membrane science

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