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Issue 29, 2013
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Inhomogeneities and local chain stretching in partially swollen networks

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Abstract

According to classic single-chain theories of rubber elasticity such as the affine or phantom models, the length N and the state of stretching R/R0 of network chains are directly reflected in the magnitude of segmental orientation correlations, as quantified by a dynamic order parameter SR2/N (this relation holds for chains in the bulk and θ solvent). S can be determined by suitable NMR techniques, and is a viable molecular probe of the network structure, as it is directly proportional to the elasticity modulus. Furthermore, previous studies (see Saalwächter et al., Soft Matter, 2013, XX, XXX, in this issue for a review) have convincingly demonstrated the validity of the phantom model for the prediction of S in equilibrium-swollen networks. We here investigate changes in the degree of local chain stretching reflected in S as a function of the degree of (partial) swelling Q = V/V0 in different networks prepared in bulk and in states of increasing dilution. Previous work has already revealed a non-monotonic dependence of S on Q, indicating strongly subaffine local deformation in the early stages of swelling. The width of the distribution in S is also accessible, and increases significantly during the early stage of swelling, indicating the well documented presence of swelling heterogeneities. We find that beyond this early stage, the network chains deform affinely. A back-extrapolation of the affine deformation range to zero swelling allows for conclusions on the actual crosslink density of the networks corrected for the effect of topological or packing constraints, which we refer to as the “phantom reference state” of a bulk network. Deviations of the network elasticity from this state constitute non-classical contributions, possible origins of which are discussed.

Graphical abstract: Inhomogeneities and local chain stretching in partially swollen networks

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Publication details

The article was received on 17 Jan 2013, accepted on 19 Mar 2013 and first published on 10 Apr 2013


Article type: Paper
DOI: 10.1039/C3SM50195G
Citation: Soft Matter, 2013,9, 6943-6954
  • Open access: Creative Commons BY-NC license
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    Inhomogeneities and local chain stretching in partially swollen networks

    W. Chassé, S. Schlögl, G. Riess and K. Saalwächter, Soft Matter, 2013, 9, 6943
    DOI: 10.1039/C3SM50195G

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