Cooperative Chain Dynamics of Tracer Chains in Highly Entangled Polyethylene Melts.

By neutron spin echo spectroscopy, we have studied the center of mass motion of short tracer chains on the molecular length scale within a highly entangled polymer matrix. The center of mass mean square displacements of the tracers independent of their molecular weight is subdiffusive at short times until it has reached the size of the tube d; then, a crossover to Fickian diffusion takes place. This observation cannot be understood within the tube model of reptation, but is rationalized as a result of important interchain couplings that lead to cooperative chain motion within the entanglement volume ∼d^{3}.

Supramolecular Dimerization in a Polymer Melt from Small-Angle X-Ray Scattering and Rheology: A Miscible Model System.

We present a structural and dynamic study on the simplest supramolecular hetero-association, recently investigated by the authors to prepare architectural homogeneous structures in the melt state, based on the bio-inspired hydrogen-bonding of thymine/diaminotriazine (thy-DAT) base-pairs. In the combination with an amorphous low T poly(butylene oxide) (PBO), no micellar structures are formed, which is expected for nonpolar polymers because of noncompatibility with the highly polar supramolecular groups. Instead, a clear polymer-like transient architecture is retrieved.

Direct Assessment of Tube Dilation in Entangled Polymers.

A key ingredient within theories focusing on the rheology of entangled polymers is the way how the topological constraints of an entangled chain are lifted by unconstrained segments, i.e., how the constraining tube is dilated.

Importance of Compact Random Walks for the Rheology of Transient Networks.

Controlling the mechanical behavior of novel supramolecular materials is of the utmost importance and requires a fundamental understanding of the underlying physical processes. We present a multimethods approach to the dynamics of entangled transient polyisoprene networks. Small-angle neutron scattering (SANS) on randomly functionalized chains shows homogeneous supramolecular melts with Gaussian chain conformations.

Molecular View on Supramolecular Chain and Association Dynamics.

The chain and association dynamics of supramolecular polymer ensembles decisively determines their properties. Using neutron spin echo (NSE) spectroscopy we present molecular insight into the space and time evolution of this dynamics. Studying a well characterized ensemble of linearly associating telechelic poly(ethylene glycol) melts carrying triple H-bonding end groups, we show that H-bond breaking significantly impacts the mode spectrum of the associates.

Nanoscale Motion of Soft Nanoparticles in Unentangled and Entangled Polymer Matrices.

We have studied the motion of polyhedral oligomeric silsesquioxane (POSS) nanoparticles modified with poly(ethylene glycol) (PEG) arms immersed in PEG matrices of different molecular weight. Employing neutron spin echo spectroscopy in combination with pulsed field gradient (PFG) NMR we found the following. (i) For entangled matrices the center of mass mean square displacement (MSD) of the PEG-POSS particles is subdiffusive following a t^{0.

Influence of the Solvent Quality on Ring Polymer Dimensions.

We present a systematic investigation of well-characterized, experimentally pure polystyrene (PS) rings with molar mass of 161 000 g/mol in dilute solutions. We measure the ring form factor at - and good-solvent conditions as well as in a polymeric solvent (linear PS of roughly comparable molar mass) by means of small-angle neutron scattering (SANS). Additional dynamic light scattering (DLS) measurements support the SANS data and help elucidate the role of solvent quality and solution preparation.

Sensing Polymer Chain Dynamics through Ring Topology: A Neutron Spin Echo Study.

Using neutron spin echo spectroscopy, we show that the segmental dynamics of polymer rings immersed in linear chains is completely controlled by the host. This transforms rings into ideal probes for studying the entanglement dynamics of the embedding matrix. As a consequence of the unique ring topology, in long chain matrices the entanglement spacing is directly revealed, unaffected by local reptation of the host molecules beyond this distance.

Celebrating Soft Matter's 10th Anniversary: Topology matters: structure and dynamics of ring polymers.

Considering topology among all polymer architectures polymer rings are unique, as they are the simplest closed structures without ends. In this review we present recent experimental advances addressing the structure and dynamics of rings. We focus mainly on neutron scattering results that reveal experimental insight on a molecular scale.

Molecular scale dynamics of large ring polymers.

We present neutron scattering data on the structure and dynamics of melts from polyethylene oxide rings with molecular weights up to ten times the entanglement mass of the linear counterpart. The data reveal a very compact conformation displaying a structure approaching a mass fractal, as hypothesized by recent simulation work. The dynamics is characterized by a fast Rouse relaxation of subunits (loops) and a slower dynamics displaying a lattice animal-like loop displacement.

Compact structure and non-Gaussian dynamics of ring polymer melts.

We present a neutron scattering analysis of the structure and dynamics of PEO polymer rings with a molecular weight 2.5 times higher than the entanglement mass. The melt structure was found to be more compact than a Gaussian model would suggest.

Direct observation of nonaffine tube deformation in strained polymer networks.

We present a one-to-one comparison of polymer segmental fluctuations as measured by small angle neutron scattering in a network under deformation with those obtained by neutron spin echo spectroscopy. This allows an independent proof of the strain dependence of the chain entanglement length. The experimentally observed nonaffine square-root dependence of the tube channel on strain is in excellent agreement with theoretical predictions and permits us to exclude an often invoked nondeformed as well as affinely deformed tube.

Effect of nanoconfinement on polymer dynamics: surface layers and interphases.

We present neutron spin echo experiments that address the much debated topic of dynamic phenomena in polymer melts that are induced by interacting with a confining surface. We find an anchored surface layer that internally is highly mobile and not glassy as heavily promoted in the literature. The polymer dynamics in confinement is, rather, determined by two phases, one fully equal to the bulk polymer and another that is partly anchored at the surface.

Viscosity of ring polymer melts.

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts to their ring counterparts at isofrictional conditions is discussed as function of the number of entanglements . In the unentangled regime is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation .

Scaling the temperature-dependent boson peak of vitreous silica with the high-frequency bulk modulus derived from Brillouin scattering data.

The position and strength of the boson peak in silica glass vary considerably with temperature T. Such variations cannot be explained solely with changes in the Debye energy. New Brillouin-scattering measurements are presented which allow determining the T dependence of unrelaxed acoustic velocities.

Cooperative dynamics in homopolymer melts: a comparison of theoretical predictions with neutron spin echo experiments.

We present a comparison between theoretical predictions of the generalized Langevin equation for cooperative dynamics (CDGLE) and neutron spin echo data of dynamic structure factors for polyethylene melts. Experiments cover an extended range of length and time scales, providing a compelling test for the theoretical approach. Samples investigated include chains with increasing molecular weights undergoing dynamics across the unentangled to entangled transition.

Inelastic neutron scattering study of methyl groups rotation in some methylxanthines.

The three isomeric dimethylxanthines and trimethylxanthine are studied by neutron spectroscopy up to energy transfers of 100 meV at energy resolutions ranging from 0.7 microeV to some meV. The loss of elastic intensity with increasing temperature can be modeled by quasielastic methyl rotation.

Quasielastic neutron scattering experiments including activation energies and mathematical modeling of methyl halide dynamics.

Quasielastic neutron scattering experiments were carried out using the multichopper time-of-flight spectrometer V3 at the Hahn-Meitner Institut, Germany and the backscattering spectrometer at Forschungszentrum Julich, Germany. Activation energies for CH(3)X, X=F, Cl, Br, and I, were obtained. In combination with results from previous inelastic neutron scattering experiments the data were taken to describe the dynamics of the halides in terms of two different models, the single particle model and the coupling model.

Polymer chain dynamics in a random environment: heterogeneous mobilities.

We present a neutron scattering investigation on a miscible blend of two polymers with greatly different glass-transition temperatures Tg. Under such conditions, the nearly frozen high-Tg component imposes a random environment on the mobile chain. The results demand the consideration of a distribution of heterogeneous mobilities in the material and demonstrate that the larger scale dynamics of the fast component is not determined by the average local environment alone.

X-ray diffraction and inelastic neutron scattering study of 1:1 tetramethylpyrazine chloranilic acid complex: temperature, isotope, and pressure effects.

The x-ray diffraction studies of the title complex were carried out at room temperature and 14 K for H/D (in hydrogen bridge) isotopomers. At 82 K a phase transition takes place leading to a doubling of unit cells and alternation of the hydrogen bond lengths linking tetramethylpyrazine (TMP) and chloranilic acid molecules. A marked H/D isotope effect on these lengths was found at room temperature.

Molecular observation of constraint release in polymer melts.

The dynamics of binary polymer blends of few labeled long chains in successively shorter matrix chains has been investigated by neutron spin echo (NSE) spectroscopy. For the first time the effect of constraint release on the chain relaxation has been directly observed on a microscopic scale. Decreasing the matrix chain length reduces the topological confinement until unconfined Rouse motion is observed, when the matrix chains are too short to confine the long chain in a tube.

A new interpretation of dielectric data in molecular glass formers.

Literature dielectric data of glycerol, propylene carbonate, and ortho-terphenyl show that the measured dielectric relaxation is a decade faster than the Debye expectation but still a decade slower than the breakdown of the shear modulus. From a comparison of time scales, the dielectric relaxation seems to be due to a process which relaxes not only the molecular orientation but also the entropy, the short range order, and the density. On the basis of this finding, we propose an alternative to the Gemant-DiMarzio-Bishop extension of the Debye picture.

Direct observation of the transition from free to constrained single-segment motion in entangled polymer melts.

We report a direct determination of the time dependent mean-squared segment displacement of a polymer chain in the melt covering the transition from free to constraint Rouse relaxation along the virtual tube of the reptation model. This has been achieved by a neutron spin-echo (NSE) measurement of the segmental self-correlation function as conveyed by the spin-incoherent scattering from two fully protonated polymer melts, polyethylene and polyethylene propylene. Within the scenario of de Gennes reptation model a transition of the time dependence of segmental mean-squared displacements from proportional, variant t(1/2) to proportional, variant t(1/4) is expected and clearly corroborated by the incoherent NSE results.

Molecular observation of contour-length fluctuations limiting topological confinement in polymer melts.

In order to study the mechanisms limiting the topological chain confinement in polymer melts, we have performed neutron-spin-echo investigations of the single-chain dynamic-structure factor from polyethylene melts over a large range of chain lengths. While at high molecular weight the reptation model is corroborated, a systematic loosening of the confinement with decreasing chain length is found. The dynamic-structure factors are quantitatively described by the effect of contour-length fluctuations on the confining tube, establishing this mechanism on a molecular level in space and time.