Andreas Wischnewski

Structure and dynamics of polymer rings by neutron scattering: breakdown of the Rouse model

We present a static and quasi-elastic neutron scattering study on both the structure and dynamics of a ring polymer in a ring and linear polymer melt, respectively. In the first case, the ring structure proved to be significantly more compact compared to the linear chain with the same molecular weight. In the mixture, the ring molecules swell as was confirmed by small angle neutron scattering (SANS) in accordance with both theory and simulation work. The dynamical behavior of both systems, which for the first time has been explored by neutron spin echo spectroscopy (NSE), shows a surprisingly fast center of mass diffusion as compared to the linear polymer. These results agree qualitatively with the presented atomistic MD simulations. The fast diffusion turned out to be an explicit violation of the Rouse model.

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. In shorter entangled matrices, where in the time frame of the experiment secondary effects such as contour length fluctuations or constraint release could play a role, the ring motion reveals that the contour length fluctuation is weaker than assumed in state-of-the-art rheology and that the constraint release is negligible. We expect that rings, as topological probes, will also grant direct access to molecular aspects of polymer motion which have been inaccessible until now within chains adhering to more complex architectures.

Neutron scattering evidence on the nature of the boson peak

Literature and unpublished neutron spectra of seven classical glass formers in the boson peak region are evaluated in terms of eigenvalue densities. The boson peak translates into a true maximum of the eigenvalue density, lying about a factor of two higher than the boson peak eigenvalue and followed by a slow decrease towards higher eigenvalues. We interpret the data in terms of a crossover from sound waves at low eigenvalues to a more or less constant eigenvalue density at high eigenvalues. The Ioffe–Regel limit of strong sound wave damping lies at the crossover eigenvalue λc, slightly higher than the boson peak. A four-parameter fit form based on the soft-potential model provides reasonable fits up to and including the beginning of the slow decrease. The parameters from the neutron data agree within their error bars with those determined from the low-temperature anomalies in the heat capacity and in the thermal conductivity. The results indicate that the strong scattering of sound waves in glasses is due to the interaction with the excess vibrational modes.

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.

Reptation in polyethylene-melts with different molecular weights

Abstract It is known since a decade that polyethylene shows a characteristic deviation from the Rouse dynamics, i.e. pronounced entanglement effects, now observable in neutron spin-echo (NSE) spectroscopy as a plateau at high Fourier times t . Earlier spin-echo data were limited to t =20–40 ns and could only determine entanglement distances but not decide between competing models. The now available time range up to 200 ns and more at the IN15 (ILL) NSE spectrometer allowed to distinguish the various models and to decide in favour of de Gennes’ Reptation model. In this model the restriction of motion originates from a trapping of the chains in a virtual tube. We present a series of new NSE-data from PE-melts at 509 K with different molecular weights between M w =12 000 g / mol and M w =190 000 g / mol extending to 170 ns that allow for the first time a systematic investigation of the reptation dynamics of PE-melts over a wide range of molecular weights.

The microscopic origin of the rheology in supramolecular entangled polymer networks

Supramolecular groups in polymeric systems lead to responsive materials which are ideally suited for applications in dynamic environments. The key to their advanced properties such as shape-memory or self-healing is the reversibility of secondary interactions which can be triggered by external stimuli such as temperature, light, or pH-value. Controlling the (mechanical) behavior of such systems requires a precise understanding of intrinsic properties. We present a multimethod study of transient polyisoprene networks that were functionalized with different amounts of hydrogen bonding urazole groups. This work aims at understanding rich rheological features on the basis of their microscopic origin. First, the thermorheological simple behavior is validated experimentally. Subsequently, we characterize the underlying microscopic processes by broadband dielectric spectroscopy ( α-process and α *-process), differential scanning calorimetry (glass transition behavior), and Fourier-transform infrared spectroscopy...

Melt dynamics of supramolecular comb polymers: Viscoelastic and dielectric response

The structure and the dynamics of supramolecular comblike polymers in the melt state is studied by a combination of linear rheology, dielectric spectroscopy, and small angle neutron scattering. The system consists of blends of 1,2-polybutyleneoxide (PBO) entangled backbones, randomly functionalized with thymine (thy) and barely entangled PBO graft chains—modified with 2,4-diamino-1,3,5-triazine (DAT) end groups. These bioinspired groups associate into a transiently branched comb architecture through heterocomplementary interaction involving the two different hydrogen bonding groups thy and DAT. In the present manuscript, we focus on the comparison of the macroscopic dynamics of the associating blends and permanent comb analogs. The viscoelastic and dielectric response of covalent and reversible combs are found to be comparable. The viscoelastic response of mixtures of thy-functionalized entangled backbones and DAT-end-modified barely entangled chains show a relaxation mechanism, which is mostly attributed...

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. Coupled motions of methyl groups seem to explain the dynamics of the methyl fluoride and chloride; however, the coupling vanishes with the increase of the mass of the halide atom in CH(3)Br and CH(3)I.

Intensity sharing between Brillouin and Umklapp scattering in glasses

The interaction between low frequency localized modes and sound waves in glasses is treated in terms of the simplest possible model, namely a single elastic dipole proportional to the displacement of the localized mode. The approximation makes it possible to calculate the contribution of the localized mode to the inelastic coherent neutron or X-ray scattering with relatively small momentum transfer. The connection to the classical second moment sum rule is discussed.

Dielectric and thermal relaxation in the energy landscape

We derive an energy landscape interpretation of dielectric relaxation times in undercooled liquids, comparing it to the traditional Debye and Gemant–DiMarzio–Bishop pictures. The interaction between different local structural rearrangements in the energy landscape explains qualitatively the recently observed splitting of the flow process into an initial and a final stage. The initial mechanical relaxation stage is attributed to hopping processes, the final thermal or structural relaxation stage to the decay of the local double-well potentials. The energy landscape concept provides an explanation for the equality of thermal and dielectric relaxation times. The equality itself is once more demonstrated on the basis of literature data for salol.