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Macromolecules
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Disentangling the Calorimetric Glass-Transition Trace in Polymer/Oligomer Mixtures from the Modeling of Dielectric Relaxation and the Input of Small-Angle Neutron Scattering

Authors: Numera Shafqat; Angel Alegría; Arantxa Arbe; Nicolas Malicki; Séverin Dronet; Lionel Porcar; Juan Colmenero;

Disentangling the Calorimetric Glass-Transition Trace in Polymer/Oligomer Mixtures from the Modeling of Dielectric Relaxation and the Input of Small-Angle Neutron Scattering

Abstract

We have disentangled the contributions to the glass transition as observed by differential scanning calorimetry (DSC) on simplified systems of industrial interest consisting of blends of styrene-butadiene rubber (SBR) and polystyrene (PS) oligomer. To do this, we have started from a model previously proposed to describe the effects of blending on the equilibrium dynamics of the α-relaxation as monitored by broadband dielectric spectroscopy (BDS). This model is based on the combination of self-concentration and thermally driven concentration fluctuations (TCFs). Considering the direct insight of small-angle neutron scattering on TCFs, blending effects on the α-relaxation can be fully accounted for by using only three free parameters: the self-concentration of the components φself SBR and φself PS) and the relevant length scale of segmental relaxation, 2R c. Their values were determined from the analysis of the BDS results on these samples, being that obtained for 2R c ≈ 25Å in the range usually reported for this magnitude in glass-forming systems. Using a similar approach, the distinct contributions to the DSC experiments were evaluated by imposing the dynamical information deduced from BDS and connecting the component segmental dynamics in the blend above the glass-transition temperature T g (at equilibrium) and the way the equilibrium is lost when cooling toward the glassy state. This connection was made through the α-relaxation characteristic time of each component at T g, τg. The agreement of such constructed curves with the experimental DSC results is excellent just assuming that τg is not affected by blending.

Country
Spain
Keywords

chain connectivity, fluctuations, alpha relaxation, component dynamics, viscosity, segmental dynamics, temperature dependence, miscible blends, length scale, time

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
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