NMR Self-Diffusion and Transverse Relaxation Time in Bitumen: The Effect of Aging

In this investigation the dynamics of two types of bitumens with different penetration grade were tested by using dynamic shear rheometry (DSR) and Nuclear Magnetic Resonance (NMR) at unaged conditions, and upon both short- and long-term artificial aging. The gel-sol transition temperature was found to increase with increasing the time of aging treatment. Arrhenius parameters of the viscosity were found, unexpectedly, to be correlated with those of simple liquids, suggesting that the two kinds of systems, although chemically and physically quite different, share the same basic process at the molecular level. The molecular dynamics has been then investigated by NMR Pulsed Field Gradient Stimulated-Echo (PFGSE) and relaxometry (Carr-Purcell-Meiboom-Gill, CPMG, spin-echo pulse sequence) to capture the effect of aging upon dynamics variables such as self-diffusion coefficients D and transverse relaxation times T₂. The translational diffusion at T> of the light molecular components of both types of bitumens was characterized by broad distributions of D which were found independent of the experimental time scale up to 0.2 s. Similarly, T₂ data could be described as a continuous unimodal distributions of relaxation times determined both at T< and T> .     

Zeroth-order optimization with orthogonal random directions

Mathematical Programming - We propose and analyze a randomized zeroth-order optimization method based on approximating the exact gradient by finite differences computed in a set of orthogonal...     

Control of macromolecular architecture of polyamides by poly-functional agents. 2. Use of oligomerization in polycondensation study

In the first paper of the series, a statistical model for star-branched polycondenzation of AB type monomers in the presence of a polyfunctional agent RA_f was completely developed. The analytical expressions obtained for the number-average (D̄P̄_n̄) and weight-average (D̄P̄_w̄) degree of polymerization, and the dispersion index (D) for whole polymer species, linear and star macromolecular chains, are now derived as function of the feed and of end-group analysis. Also the important molecular parameter, mole fraction of star-branched polymer, can be evaluated. Some numerical examples are presented. It is illustrated that the molecular weight properties of the linear and star-branched polymers in the mixture of the products, very important factors for the application of this kind of polymeric materials, can be determined starting from the feed and terminal group analysis. Polymerization and oligomerization of 6-aminocaproic acid were carried out in the presence of trimesic (T3) acid and 2,2,6,6-tetra(β-carboxyethyl)cyclohexanone (T4) and EDTA as tri- and terra-functional agents. The molecular weights calculated are in good agreement with those obtained by Size Exclusion Chromatography (SEC), end group analysis and NMR spectra.