Biomedical subjects

R Stepanyan

Publications and source records attributed to R Stepanyan.

5 recordsLinked to original sources

PubMed2005

Flow-induced correlation effects within a linear chain in a polymer melt.

A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present model allows one to take into account all the major relaxation mechanisms. Special cases of the derived set of equations are shown to yield existing models and shed some light on the connection between them. Consequences of several assumptions widely used in the literature are analyzed within the developed framework.

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PubMed2005

A molecular model for cohesive slip at polymer melt/solid interfaces.

A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulk+boundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.

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PubMed2005

Influence of molecular weight on the phase behavior and structure formation of branched side-chain hairy-rod polyfluorene in bulk phase.

We report on an experimental study of the self-organization and phase behavior of hairy-rod pi -conjugated branched side-chain polyfluorene, poly[9,9-bis(2-ethylhexyl)-fluorene-2,7-diyl]-i.e., poly[2,7-(9,9-bis(2-ethylhexyl)fluorene] (PF2/6) -as a function of molecular weight (M(n)) . The results have been compared to those of phenomenological theory. Samples for which M(n) =3-147 kg/mol were used. First, the stiffness of PF2/6 , the assumption of the theory, has been probed by small-angle neutron scattering in solution. Thermogravimetry has been used to show that PF2/6 is thermally stable over the conditions studied. Second, the existence of nematic and hexagonal phases has been phenomenologically identified for lower and higher M(n) (LMW, M(n) < M(*)(n) and HMW, M(n) > M(*)(n) ) regimes, respectively, based on free-energy argument of nematic and hexagonal hairy rods and found to correspond to the experimental x-ray diffraction (XRD) results for PF2/6 . By using the lattice parameters of PF2/6 as an experimental input, the nematic-hexagonal transition has been predicted in the vicinity of glassification temperature (T(g)) of PF2/6 . Then, by taking the orientation parts of the free energies into account the nematic-hexagonal transition has been calculated as a function of temperature and M(n) and a phase diagram has been formed. Below T(g) of 80 degrees C only (frozen) nematic phase is observed for M(n)< M(*)(n) = 10(4) g/mol and crystalline hexagonal phase for M(n) > M(*)(n) . The nematic-hexagonal transition upon heating is observed for the HMW regime depending weakly on M(n) , being at 140-165 degrees C for M(n) > M(*)(n). Third, the phase behavior and structure formation as a function of M(n) have been probed using powder and fiber XRD and differential scanning calorimetry and reasonable semiquantitative agreement with theory has been found for M(n) >or=3 kg/mol. Fourth, structural characteristics are widely discussed. The nematic phase of LMW materials has been observed to be denser than high-temperature nematic phase of HMW compounds. The hexagonal phase has been found to be paracrystalline in the (ab0) plane but a genuine crystal meridionally. We also find that all these materials including the shortest 10-mer possess the formerly observed rigid five-helix hairy-rod molecular structure.

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PubMed2003

Phase behavior and structure formation of hairy-rod supramolecules.

Phase behavior and microstructure formation of rod and coil molecules, which can associate to form hairy-rod polymeric supramolecules, are addressed theoretically. Association induces considerable compatibility enhancement between the rod and coil molecules and various microscopically ordered structures can appear in the compatibility region. The equilibria between microphase-separated states, the coil-rich isotropic liquid and the rod-rich nematic are discussed in detail. In the regime where hairy-rod supramolecules with a high grafting density appear as a result of the association, three phase diagram types are possible depending on the value of the association energy. In the low grafting density regime only the lamellar microstructure is proven to be stable.

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PubMed2001

Strongly adsorbed comb copolymers with rigid side chains.

We study the conformational behavior in a plane of a comb copolymer molecule, consisting of a semiflexible backbone and rigid side chains interacting via a van der Waals potential. Using a mean-field approach, two different regimes are distinguished depending on the strength of the attraction between the side chains. In the weak attraction limit the side chains are oriented preferably perpendicular to the backbone. The persistence length lambda of the comb copolymer molecule scales as the second power of the length of the side chain L: lambda is proportional to L2. In the strong attraction limit all side chains become strongly tilted and the persistence length scales as lambda is proportional to L4. The nonlinear bending regime is also studied and characterized by a change in structure and a decreasing moment of bending force as a function of curvature, i.e., bending becomes easier.

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