This work consists of two separate projects unified by the idea to extend the Discrete Slip-Link Model, which has been being successfully... Show moreThis work consists of two separate projects unified by the idea to extend the Discrete Slip-Link Model, which has been being successfully developed in this group to predict rheological behavior of entangled flexible polymers, to new applications. The first project was dedicated to application of the Discrete Slip-Link Model to dielectric relaxation in order to simultaneously predict linear rheology and dielectric relaxation experiments of entangled polyisoprenes. Linear monodisperse, linear bidisperse and star-branched monodisperse systems were studied. It was found that all circumstances save one are well described. Namely, dilute long chains in a sea of short chains can be predicted rheologically, but dielectric relaxation data show a reduction in the relaxation time of long chains greater than that predicted by either the DSM or the expected Rouse motion. The second project was focused on the derivation of the exact free energy expression for semiflexible chains in the presence of entanglements in order to implement the DSM for semiflexible polymers. The special cases of chains with one, two and three strands are examined. An additional implementation of obtained results for one and two strands to buckling instability was performed. It is believed that in two dimensional case the critical buckling force is increased by thermal fluctuations in comparison to classical Euler buckling. However, how the critical buckling force is influenced by thermal fluctuations in three dimensions remains unclear. Some research groups calculate the critical buckling force approximately and conclude that, in opposite to 2D case, in 3D the force is decreased by thermal fluctuations. In this work the critical buckling force for semiflexible chain under compression was calculated exactly. It was shown that thermal fluctuations significantly increase the critical force over classical Euler buckling force in both two and three dimensions. Ph.D. in Chemical Engineering, May 2015 Show less
