Modelle für die Durchdringung von Knäuelmolekülen aus Lichtstreuungsmessungen

Light scattering, neutron scattering and viscosity measurements on a nematic and a smectic polymethacrylate demonstrate the presence of molecularly disperse coils in solution. For the nematic polymer, toluene is a theta solvent, the behaviour familiar from conventional polymers (unperturbed coil conformation) being exhibited at the theta point. The isotropic melts likewise contain unperturbed coils; in the case of the nematic polymers, however, the coils in the melt have a radius of gyration which is about 30% smaller than that in solution at the theta point. In the liquid-crystalline phase, the mean radii of gyration in both cases are identical to the corresponding parameters in the isotro…

Theoretical relations for the dependence of the z-average radius of gyration Rz as a function of the mass average molar mass Mw are derived for expanded coils, persistence coils with persistence of direction, persistence coils with persistence of direction and curvature, and for needles, all exhibiting a Schulz-distribution of their molar masses. These relations are applied to experimental data from light scattering of polystyrene in toluene and DNA-Na in aqueous NaCl-solution of 200 mol NaCl per m3 at room temperature. In the case of DNA it becomes evident that the double helix shows no important persistence of curvature and that the experimental data can be described adequately by a persi…

Röntgenkleinwinkelstreuung an gelöster desoxyribonucleinsäure in einem weiten winkelbereich

Samples of ring and open chain polystyrene in dilute perdeuterated toluene solution were measured by small angle neutron scattering up to a value of the scattering vector Q = 2 nm−1. The molar masses 12000 ≤ M/(g/mol) ≤ 22000, the mean square radii of gyration 〈R2〉 and the second virial coefficients A2 of the samples were determined. The results are compared to theories which describe the dependencies 〈R2〉 = f(M) and A2 = f(M) for both cyclic and linear chain molecules. A qualitative agreement between theory and experiment is obtained.

Provided a polymer is soluble, i. e., molecularly dispersed in another polymer irrespective of the molecular weight of the components, the solution is exothermic. By increasing the temperature two effects, both unfavourable to mixing become larger: (i) the excess entropy of mixing caused by contact interaction and (ii) the total effect from the difference of the free volumes of the pure components. So, an upper miscibility gap occurs. The thermodynamic properties of the mixture cannot be derived from the properties of the pure components. They can be described by the corresponding states theory of Prigogine, Flory, and Patterson with suitable values for the contact energy and contact entrop…