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Statements

Subject Item
n2:RIV%2F00216208%3A11320%2F14%3A10285407%21RIV15-MSM-11320___
rdf:type
skos:Concept n9:Vysledek
rdfs:seeAlso
http://dx.doi.org/10.1021/ma5006217
dcterms:description
In certain real situations, polymer networks cannot swell freely but are subjected to constraints by action of external forces or geometric restrictions. In this contribution, the restriction to swelling by adhesion of a cross-linked polymer film deposited on a rigid substrate is considered. Such constraints prevent swelling in plane, and the osmotic force concentrates on extension of network chains in the direction normal to the surface. We analyze existing rubber elasticity models taking into account finite extensibility of network chains and derive the elastic contribution to the chemical potential of the solvent in swollen networks. For the mixing contribution to the change of the Gibbs energy, it is more appropriate to consider the network containing cross-links, but with undeformed network chains than an un-cross-linked polymer of infinite degree of polymerization, because continuing formation of bonds within an infinite molecule further decreases the entropy. The additional term is proportional to the cycle rank of the network. The reformulation of the mixing contribution is important for consideration of cross-linking induced phase separation during network formation. The phase separation limit is due to the cross-link contribution to the mixing part of the Gibbs energy and has nothing to do with chain stretching. The swelling theories respecting finite extensibility of network chains are then applied to cross-linked poly(ethylene oxide) films obtained by plasma-assisted vapor deposition with the aim to determine their effective cross-link density. In certain real situations, polymer networks cannot swell freely but are subjected to constraints by action of external forces or geometric restrictions. In this contribution, the restriction to swelling by adhesion of a cross-linked polymer film deposited on a rigid substrate is considered. Such constraints prevent swelling in plane, and the osmotic force concentrates on extension of network chains in the direction normal to the surface. We analyze existing rubber elasticity models taking into account finite extensibility of network chains and derive the elastic contribution to the chemical potential of the solvent in swollen networks. For the mixing contribution to the change of the Gibbs energy, it is more appropriate to consider the network containing cross-links, but with undeformed network chains than an un-cross-linked polymer of infinite degree of polymerization, because continuing formation of bonds within an infinite molecule further decreases the entropy. The additional term is proportional to the cycle rank of the network. The reformulation of the mixing contribution is important for consideration of cross-linking induced phase separation during network formation. The phase separation limit is due to the cross-link contribution to the mixing part of the Gibbs energy and has nothing to do with chain stretching. The swelling theories respecting finite extensibility of network chains are then applied to cross-linked poly(ethylene oxide) films obtained by plasma-assisted vapor deposition with the aim to determine their effective cross-link density.
dcterms:title
Constrained Swelling of Polymer Networks: Characterization of Vapor-Deposited Cross-Linked Polymer Thin Films Constrained Swelling of Polymer Networks: Characterization of Vapor-Deposited Cross-Linked Polymer Thin Films
skos:prefLabel
Constrained Swelling of Polymer Networks: Characterization of Vapor-Deposited Cross-Linked Polymer Thin Films Constrained Swelling of Polymer Networks: Characterization of Vapor-Deposited Cross-Linked Polymer Thin Films
skos:notation
RIV/00216208:11320/14:10285407!RIV15-MSM-11320___
n5:aktivita
n19:P n19:I
n5:aktivity
I, P(GAP101/12/1306), P(LD12066)
n5:cisloPeriodika
13
n5:dodaniDat
n10:2015
n5:domaciTvurceVysledku
n18:9253378 n18:4603443
n5:druhVysledku
n17:J
n5:duvernostUdaju
n6:S
n5:entitaPredkladatele
n16:predkladatel
n5:idSjednocenehoVysledku
8678
n5:idVysledku
RIV/00216208:11320/14:10285407
n5:jazykVysledku
n14:eng
n5:klicovaSlova
terpolymers; microstructures; instabilities; swollen; hydrogel layers; constitutive models; poly(ethylene glycol); non-gaussian chains; rubber elasticity model; finite chain extensibility
n5:klicoveSlovo
n8:microstructures n8:instabilities n8:hydrogel%20layers n8:terpolymers n8:rubber%20elasticity%20model n8:constitutive%20models n8:finite%20chain%20extensibility n8:swollen n8:poly%28ethylene%20glycol%29 n8:non-gaussian%20chains
n5:kodStatuVydavatele
US - Spojené státy americké
n5:kontrolniKodProRIV
[F5F5677F5FB2]
n5:nazevZdroje
Macromolecules
n5:obor
n20:CD
n5:pocetDomacichTvurcuVysledku
2
n5:pocetTvurcuVysledku
4
n5:projekt
n11:LD12066 n11:GAP101%2F12%2F1306
n5:rokUplatneniVysledku
n10:2014
n5:svazekPeriodika
47
n5:tvurceVysledku
Shukurov, Andrey Dušek, Karel Duskova-Smrckova, Miroslava Biederman, Hynek
n5:wos
000338806400030
s:issn
0024-9297
s:numberOfPages
11
n15:doi
10.1021/ma5006217
n12:organizacniJednotka
11320