Ion and polymer dynamics in polymer electrolytes PPO-LiClO4: II. 2H and 7Li NMR stimulated-echo experiment

We use 2H NMR stimulated-echo spectroscopy to measure two-time correlation functions characterizing the polymer segmental motion in polymer electrolytes PPO-LiClO4 near the glass transition temperature Tg. To investigate effects of the salt on the polymer dynamics, we compare results for different ether oxygen to lithium ratios, namely, 6:1, 15:1, 30:1 and infinity. For all compositions, we find nonexponential correlation functions, which can be described by a Kohlrausch function. The mean correlation times show quantitatively that an increase of the salt concentration results in a strong slowing down of the segmental motion. Consistently, for the high 6:1 salt concentration, a high apparent activation energy E_a=4.1eV characterizes the temperature dependence of the mean correlation times at Tg < T< 1.1T_g, while smaller values E_a=2.5eV are observed for moderate salt contents. The correlation functions are most nonexponential for 15:1 PPO-LiClO4, whereas the stretching is reduced for higher and lower salt concentrations. A similar dependence of the correlation functions on the evolution time in the presence and in the absence of ions indicates that addition of salt hardly affects the reorientational mechanism. For all compositions, mean jump angles of about 15 degree characterize the segmental reorientation. In addition, comparison of results from 2H and 7Li NMR stimulated-echo experiments suggests a coupling of ion and polymer dynamics in 15:1 PPO-LiClO4.Comment: 14 pages, 12 figure

Dynamic heterogeneities in the out-of-equilibrium dynamics of simple spherical spin models

The response of spherical two-spin interaction models, the spherical ferromagnet (s-FM) and the spherical Sherrington-Kirkpatrick (s-SK) model, is calculated for the protocol of the so-called nonresonant hole burning experiment (NHB) for temperatures below the respective critical temperatures. It is shown that it is possible to select dynamic features in the out-of-equilibrium dynamics of both models, one of the hallmarks of dynamic heterogeneities. The behavior of the s-SK model and the s-FM in three dimensions is very similar, showing dynamic heterogeneities in the long time behavior, i.e. in the aging regime. The appearence of dynamic heterogeneities in the s-SK model explicitly demonstrates that these are not necessarily related to {\it spatial} heterogeneities. For the s-FM it is shown that the nature of the dynamic heterogeneities changes as a function of dimensionality. With incresing dimension the frequency selectivity of the NHB diminishes and the dynamics in the mean-field limit of the s-FM model becomes homogeneous.Comment: 16 pages, 8 figure

Dynamical heterogeneities in a supercooled Lennard-Jones liquid

We present the results of a large scale molecular dynamics computer simulation study in which we investigate whether a supercooled Lennard-Jones liquid exhibits dynamical heterogeneities. We evaluate the non-Gaussian parameter for the self part of the van Hove correlation function and use it to identify ``mobile'' particles. We find that these particles form clusters whose size grows with decreasing temperature. We also find that the relaxation time of the mobile particles is significantly shorter than that of the bulk, and that this difference increases with decreasing temperature.Comment: 8 pages of RevTex, 4 ps figure

Growing Correlation Length on Cooling Below the Onset of Caging in a Simulated Glass-Forming Liquid

We present a calculation of a fourth-order, time-dependent density correlation function that measures higher-order spatiotemporall correlations of the density of a liquid. From molecular dynamics simulations of a glass-forming Lennard-Jones liquid, we find that the characteristic length scale of this function has a maximum as a function of time which increases steadily beyond the characteristic length of the static pair correlation function $g(r)$ in the temperature range approaching the mode coupling temperature from above

Transitions/relaxations in polyester adhesive/PET system

The correlations between the transitions and the dielectric relaxation processes of the oriented poly(ethylene terephthalate) (PET) pre-impregnated of the polyester thermoplastic adhesive have been investigated by differential scanning calorimetry (DSC) and dynamic dielectric spectroscopy (DDS). The thermoplastic polyester adhesive and the oriented PET films have been studied as reference samples. This study evidences that the adhesive chain segments is responsible for the physical structure evolution in the PET-oriented film. The transitions and dielectric relaxation modes’ evolutions in the glass transition region appear characteristic of the interphase between adhesive and PET film, which is discussed in terms of molecular mobility. The storage at room temperature of the adhesive tape involves the heterogeneity of the physical structure, characterized by glass transition dissociation. Thus, the correlation between the transitions and the dielectric relaxation processes evidences a segregation of the amorphous phases. Therefore, the physical structure and the properties of the material have been linked to the chemical characteristics

Transitions between Inherent Structures in Water

The energy landscape approach has been useful to help understand the dynamic properties of supercooled liquids and the connection between these properties and thermodynamics. The analysis in numerical models of the inherent structure (IS) trajectories -- the set of local minima visited by the liquid -- offers the possibility of filtering out the vibrational component of the motion of the system on the potential energy surface and thereby resolving the slow structural component more efficiently. Here we report an analysis of an IS trajectory for a widely-studied water model, focusing on the changes in hydrogen bond connectivity that give rise to many IS separated by relatively small energy barriers. We find that while the system \emph{travels} through these IS, the structure of the bond network continuously modifies, exchanging linear bonds for bifurcated bonds and usually reversing the exchange to return to nearly the same initial configuration. For the 216 molecule system we investigate, the time scale of these transitions is as small as the simulation time scale ($\approx 1$ fs). Hence for water, the transitions between each of these IS is relatively small and eventual relaxation of the system occurs only by many of these transitions. We find that during IS changes, the molecules with the greatest displacements move in small ``clusters'' of 1-10 molecules with displacements of $\approx 0.02-0.2$ nm, not unlike simpler liquids. However, for water these clusters appear to be somewhat more branched than the linear ``string-like'' clusters formed in a supercooled Lennar d-Jones system found by Glotzer and her collaborators.Comment: accepted in PR

Elastic scattering of 11,8 MEV deuterons from several elements

The angular distributions of 11.8 MeV deuterons elastically scattered from C, Mg, Al, Ti, Fe, Ni, Cu, Zn, Zr, Nb, Rh, Pd, Ag, Cd, In, Sn, Ta and Au have been measured. The detector is capable of electronically separating deuterons from other ions which may enter the detector. The data has been taken in 2 degree steps between 20° and 165°. The structure in the angular distribution observed with the light target elements vanishes with increasing atomic weight. An exception is observed between A=90 and A=120

String-like Clusters and Cooperative Motion in a Model Glass-Forming Liquid

A large-scale molecular dynamics simulation is performed on a glass-forming Lennard-Jones mixture to determine the nature of dynamical heterogeneities which arise in this model fragile liquid. We observe that the most mobile particles exhibit a cooperative motion in the form of string-like paths (``strings'') whose mean length and radius of gyration increase as the liquid is cooled. The length distribution of the strings is found to be similar to that expected for the equilibrium polymerization of linear polymer chains.Comment: 6 pages of RevTex, 6 postscript figures, uses epsf.st

Nanometer Scale Dielectric Fluctuations at the Glass Transition

Using non-contact scanning probe microscopy (SPM) techniques, dielectric properties were studied on 50 nanometer length scales in poly-vinyl-acetate (PVAc) films in the vicinity of the glass transition. Low frequency (1/f) noise observed in the measurements, was shown to arise from thermal fluctuations of the electric polarization. Anomalous variations observed in the noise spectrum provide direct evidence for cooperative nano-regions with heterogeneous kinetics. The cooperative length scale was determined. Heterogeneity was long-lived only well below the glass transition for faster than average processes.Comment: 4 pages, 4 embedded PS figures, RevTeX - To appear in Phys. Rev. Let

Morphology of supported polymer electrolyte ultra-thin films: a numerical study

Morphology of polymer electrolytes membranes (PEM), e.g., Nafion, inside PEM fuel cell catalyst layers has significant impact on the electrochemical activity and transport phenomena that determine cell performance. In those regions, Nafion can be found as an ultra-thin film, coating the catalyst and the catalyst support surfaces. The impact of the hydrophilic/hydrophobic character of these surfaces on the structural formation of the films has not been sufficiently explored yet. Here, we report about Molecular Dynamics simulation investigation of the substrate effects on the ionomer ultra-thin film morphology at different hydration levels. We use a mean-field-like model we introduced in previous publications for the interaction of the hydrated Nafion ionomer with a substrate, characterized by a tunable degree of hydrophilicity. We show that the affinity of the substrate with water plays a crucial role in the molecular rearrangement of the ionomer film, resulting in completely different morphologies. Detailed structural description in different regions of the film shows evidences of strongly heterogeneous behavior. A qualitative discussion of the implications of our observations on the PEMFC catalyst layer performance is finally proposed