Measuring and predicting the dynamics of linear monodisperse entangled polymers in rapid flow through an abrupt contraction. A small angle neutron scattering study

Small-angle neutron scattering measurements on a series of monodisperse linear entangled polystyrene melts in nonlinear flow through an abrupt 4:1 contraction have been made. Clear signatures of melt deformation and subsequent relaxation can be observed in the scattering patterns, which were taken along the centerline. These data are compared with the predictions of a recently derived molecular theory. Two levels of molecular theory are used: a detailed equation describing the evolution of molecular structure over all length scales relevant to the scattering data and a simplified version of the model, which is suitable for finite element computations. The velocity field for the complex melt flow is computed using the simplified model and scattering predictions are made by feeding these flow histories into the detailed model. The modeling quantitatively captures the full scattering intensity patterns over a broad range of data with independent variation of position within the contraction geometry, bulk flow rate and melt molecular weight. The study provides a strong, quantitative validation of current theoretical ideas concerning the microscopic dynamics of entangled polymers which builds upon existing comparisons with nonlinear mechanical stress data. Furthermore, we are able to confirm the appreciable length scale dependence of relaxation in polymer melts and highlight some wider implications of this phenomenon.

On the absolute calibration of bench-top small-angle X-ray scattering instruments: a comparison of different standard methods

Absolute calibration relates the measured (arbitrary) intensity to the differential scattering cross section of the sample, which contains all of the quantitative information specific to the material. The importance of absolute calibration in small-angle scattering experiments has long been recognized. This work details the absolute calibration procedure of a small-angle X-ray scattering instrument from Bruker AXS. The absolute calibration presented here was achieved by using a number of different types of primary and secondary standards. The samples were: a glassy carbon specimen, which had been independently calibrated from neutron radiation; a range of pure liquids, which can be used as primary standards as their differential scattering cross section is directly related to their isothermal compressibility; and a suspension of monodisperse silica particles for which the differential scattering cross section is obtained from Porod's law. Good agreement was obtained between the different standard samples, provided that care was taken to obtain significant signal averaging and all sources of background scattering were accounted for. The specimen best suited for routine calibration was the glassy carbon sample, due to its relatively intense scattering and stability over time; however, initial calibration from a primary source is necessary. Pure liquids can be used as primary calibration standards, but the measurements take significantly longer and are, therefore, less suited for frequent use.

Neutron-mapping polymer flow: Scattering, flow visualization, and molecular theory

Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent tube model molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.

Molecular dynamics characterization of n-octyl-beta-D-glucopyranoside micelle structure in aqueous solution

n-Octyl-beta-D-glueopyranoside (OG) is a non-ionic glycolipid, which is used widely in biotechnical and biochemical applications. All-atom molecular dynamics simulations from two different initial coordinates and velocities in explicit solvent have been performed to characterize the structural behaviour of an OG aggregate at equilibrium conditions. Geometric packing properties determined from the simulations and small angle neutron scattering experiment state that OG micelles are more likely to exist in a non-spherical shape, even at the concentration range near to the critical micelle concentration (0.025 M). Despite few large deviations in the principal moment of inertia ratios, the average micelle shape calculated from both simulations is a prolate ellipsoid. The deviations at these time scales are presumably the temporary shape change of a micelle. However, the size of the micelle and the accessible surface areas were constant during the simulations with the micelle surface being rough and partially elongated. Radial distribution functions computed for the hydroxyl oxygen atoms of an OG show sharper peaks at a minimum van der Waals contact distance than the acetal oxygen, ring oxygen, and anomeric carbon atoms. This result indicates that these atoms are pointed outwards at the hydrophilic/hydrophobic interface, form hydrogen bonds with the water molecules, and thus hydrate the micelle surface effectively. (c) 2005 Elsevier Inc. All rights reserved.

Effect of the average soft-segment length on the morphology and properties of segmented polyurethane nanocomposites

Two organically modified layered silicates (with small and large diameters) were incorporated into three segmented polyurethanes with various degrees of microphase separation. Microphase separation increased with the molecular weight of the poly(hexamethylene oxide) soft segment. The molecular weight of the soft segment did not influence the amount of polyurethane intercalating the interlayer spacing. Small-angle neutron scattering and differential scanning calorimetry data indicated that the layered silicates did not affect the microphase morphology of any host polymer, regardless of the particle diameter. The stiffness enhancement on filler addition increased as the microphase separation of the polyurethane decreased, presumably because a greater number of urethane linkages were available to interact with the filler. For comparison, the small nanofiller was introduced into a polyurethane with a poly(tetramethylene oxide) soft segment, and a significant increase in the tensile strength and a sharper upturn in the stress-strain curve resulted. No such improvement occurred in the host polymers with poly(hexamethylene oxide) soft segments. It is proposed that the nanocomposite containing the more hydrophilic and mobile poly(tetramethylene oxide) soft segment is capable of greater secondary bonding between the polyurethane chains and the organosilicate surface, resulting in improved stress transfer to the filler and reduced molecular slippage. (c) 2006 Wiley Periodicals, Inc.