The deuteron transverse relaxation properties of polyethylene oxide melts of four different molecular weights, covering the range from the onset of entanglements to the regime of fully entangled chains, are investigated using Hahn echo decays over an extensive time interval up to ten times the effective transverse spin relaxation time. The results are compared to predictions based on the Rouse and reptation formalisms, taking into account the dynamical heterogeneity of linear polymer chains produced by the end segments. The experimental results can be described qualitatively by a combination of both models, with the contribution of reptation dynamics increasing with growing chain length. The transition is continuous, rather than being characterized by sharp regime boundaries. Up to a molecular weight of 300.000 g/mol, the predicted limit of pure reptation dynamics is not yet reached. Quantitative deviations from the predicted decays as computed by numerical procedures become observable toward the long-time limit of the Hahn echo decays and are being discussed in terms of shortcomings of the available reptation theories.
The distribution of NMR relaxation times and diffusion coefficients in crude oils results from the vast number of different chemical species. In addition, the presence of asphaltenes provides different relaxation environments for the maltenes, generated by steric hindrance in the asphaltene aggregates and possibly by the spatial distribution of radicals. Since the dynamics of the maltenes is further modified by the interactions between maltenes and asphaltenes, these interactions—either through steric hindrances or promoted by aromatic-aromatic interactions—are of particular interest. Here, we aim at investigating the interaction between individual protonic and deuterated maltene species of different molecular size and aromaticity and the asphaltene macroaggregates by comparing the maltenes’ NMR relaxation (T1 and T2) and translational diffusion (D) properties in the absence and presence of the asphaltene in model solutions. The ratio of the average transverse and longitudinal relaxation rates, describing the non-exponential relaxation of the maltenes in the presence of the asphaltene, and its variation with respect to the asphaltene-free solutions are discussed. The relaxation experiments reveal an apparent slowing down of the maltenes’ dynamics in the presence of asphaltenes, which differs between the individual maltenes. While for single-chained alkylbenzenes, a plateau of the relaxation rate ratio was found for long aliphatic chains, no impact of the maltenes’ aromaticity on the maltene–asphaltene interaction was unambiguously found. In contrast, the reduced diffusion coefficients of the maltenes in presence of the asphaltenes differ little and are attributed to the overall increased viscosity.
Spatial displacements of spins between radio frequency pulses in a Double-Quantum (DQ) NMR pulse sequence generate additional terms in the effective DQ Hamiltonian. We derive a simple expression allowing the estimation and control of these contributions to the initial rise of the DQ build up function by variation of experimental parameters in systems performing anomaleouse diffusion. The application to polymers is discussed.
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