How Do Organic Vapors Swell Ultra-Thin PIM-1 Films?

Handle URI:
http://hdl.handle.net/10754/625181
Title:
How Do Organic Vapors Swell Ultra-Thin PIM-1 Films?
Authors:
Ogieglo, Wojciech; Rahimi, Khosrow; Rauer, Sebastian Bernhard; Ghanem, Bader ( 0000-0002-2044-2434 ) ; Ma, Xiao-Hua; Pinnau, Ingo ( 0000-0003-3040-9088 ) ; Wessling, Matthias
Abstract:
Dynamic sorption of ethanol and toluene vapor into ultra-thin supported PIM-1 films down to 6 nm are studied with a combination of in-situ spectroscopic ellipsometry and in-situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to thicker films. Second, at low penetrant activities (below 0.3 p/p0) films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite similar swelling magnitude. Third, for the ultra-thin films the onset of the dynamic penetrant-induced glass transition Pg has been found to shift to higher values indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the super-glassy PIM-1 at the substrate surface leads to an arrested, even more rigid and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion the surface seems to plasticize earlier than the bulk and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.
KAUST Department:
Advanced Membranes and Porous Materials Research Center
Citation:
Ogieglo W, Rahimi K, Rauer SB, Ghanem BS, Ma X-H, et al. (2017) How Do Organic Vapors Swell Ultra-Thin PIM-1 Films? The Journal of Physical Chemistry B. Available: http://dx.doi.org/10.1021/acs.jpcb.7b03891.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry B
KAUST Grant Number:
SEED Fund OSR-2015-SEED-2445-01
Issue Date:
22-Jun-2017
DOI:
10.1021/acs.jpcb.7b03891
Type:
Article
ISSN:
1520-6106; 1520-5207
Sponsors:
This publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. SEED Fund OSR-2015-SEED-2445-01.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.7b03891
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center

Full metadata record

DC FieldValue Language
dc.contributor.authorOgieglo, Wojciechen
dc.contributor.authorRahimi, Khosrowen
dc.contributor.authorRauer, Sebastian Bernharden
dc.contributor.authorGhanem, Baderen
dc.contributor.authorMa, Xiao-Huaen
dc.contributor.authorPinnau, Ingoen
dc.contributor.authorWessling, Matthiasen
dc.date.accessioned2017-07-12T07:20:55Z-
dc.date.available2017-07-12T07:20:55Z-
dc.date.issued2017-06-22en
dc.identifier.citationOgieglo W, Rahimi K, Rauer SB, Ghanem BS, Ma X-H, et al. (2017) How Do Organic Vapors Swell Ultra-Thin PIM-1 Films? The Journal of Physical Chemistry B. Available: http://dx.doi.org/10.1021/acs.jpcb.7b03891.en
dc.identifier.issn1520-6106en
dc.identifier.issn1520-5207en
dc.identifier.doi10.1021/acs.jpcb.7b03891en
dc.identifier.urihttp://hdl.handle.net/10754/625181-
dc.description.abstractDynamic sorption of ethanol and toluene vapor into ultra-thin supported PIM-1 films down to 6 nm are studied with a combination of in-situ spectroscopic ellipsometry and in-situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to thicker films. Second, at low penetrant activities (below 0.3 p/p0) films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite similar swelling magnitude. Third, for the ultra-thin films the onset of the dynamic penetrant-induced glass transition Pg has been found to shift to higher values indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the super-glassy PIM-1 at the substrate surface leads to an arrested, even more rigid and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion the surface seems to plasticize earlier than the bulk and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.en
dc.description.sponsorshipThis publication is based upon work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. SEED Fund OSR-2015-SEED-2445-01.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jpcb.7b03891en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry B, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.jpcb.7b03891.en
dc.titleHow Do Organic Vapors Swell Ultra-Thin PIM-1 Films?en
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.identifier.journalThe Journal of Physical Chemistry Ben
dc.eprint.versionPost-printen
dc.contributor.institutionDWI-Leibniz Institute for Interactive Materials, Forckenbeckstr. 50, 52074 Aachen, Germanyen
kaust.authorGhanem, Baderen
kaust.authorMa, Xiao-Huaen
kaust.authorPinnau, Ingoen
kaust.grant.numberSEED Fund OSR-2015-SEED-2445-01en
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