Dynamics of water-alcohol mixtures: insights from nuclear magnetic resonance, broadband dielectric spectroscopy, and triplet solvation dynamics.

We combine (2)H nuclear magnetic resonance (NMR), broadband dielectric spectroscopy (BDS), and triplet solvation dynamics (TSD) to investigate molecular dynamics in glass-forming mixtures of water and propylene glycol in very broad time and temperature ranges. All methods yield consistent results for the α process of the studied mixtures, which hardly depends on the composition and shows Vogel-Fulcher temperature dependence as well as Cole-Davidson spectral shape. The good agreement between BDS and TDS data reveals that preferential solvation of dye molecules in microheterogeneous mixtures does not play an important role. Below the glass transition temperature T(g), NMR and BDS studies reveal that the ß process of the mixtures shows correlation times, which depend on the water concentration, but exhibit a common temperature dependence, obeying an Arrhenius law with an activation energy of E(a) = 0.54 eV, as previously reported for mixtures of water with various molecular species. Detailed comparison of NMR and BDS correlation functions for the ß process unravels that the former decay faster and more stretched than the latter. Moreover, the present NMR data imply that propylene glycol participates in the ß process and, hence, it is not a pure water process, and that the mechanism for molecular dynamics underlying the ß process differs in mixtures of water with small and large molecules.

Polymer-induced transient networks in water-in-oil microemulsions studied by small-angle x-ray and dynamic light scattering.

We study water-in-oil microemulsions, in particular dispersions of water droplets coated with a monolayer of the anionic surfactant AOT in a continuous phase of n -decane. Upon addition of the amphiphilic triblock copolymer PEO(polyethylenoxide)-PI(polyisoprene)-PEO, a transient network is formed. At constant droplet size we vary the polymer concentration and there is clear evidence for an increasing crosslinking of the droplets from structural investigations with small-angle x-ray scattering. The dynamics of concentration fluctuations consisting of the translational diffusion of the droplets and the relaxation of the network are monitored with photon correlation spectroscopy. We mainly focus on the variation of the dynamic behavior as a function of the number of polymer molecules per droplet and the droplet volume fraction, which may be taken as a measure for the interdroplet distance. With increasing polymer content the dynamics of the system slows down and three different relaxation processes may be distinguished. We discuss the origin of the different relaxation modes. In particular, it turns out that the intermediate relaxation mode may be suppressed by index matching the oil matrix and the PI block and that it is effectively slowed down by an additional loading of the emulsion droplets with polyethylene glycol of increasing molecular weight.

Reexamination of the evolution of the dynamic susceptibility of the glass former glycerol.

The dielectric data of glycerol compiled by Lunkenheimer et al. [Contemp. Phys. 41, 15 (2000)] are reanalyzed within a phenomenological approach on the one hand, and within mode coupling theory (MCT), on the other. We present a complete interpolation of the dielectric data covering 17 decades in frequencies. The crossover temperature extracted from the phenomenological analysis of the slow response at low temperatures and defined by the emergence of the excess wing upon cooling agrees well with the critical temperature extracted from a MCT analysis of the dynamics at high temperatures including data that were not used in the first MCT analysis of glycerol by Lunkenheimer et al. [Phys. Rev. Lett. 77, 318 (1996)]. The crossover temperature is found to be T(c)=288+/-3 K, which is significantly higher than previously reported. Extracting the nonergodicity parameter f, the characteristic anomaly is only found when 1-f is inspected, since f is very close to 1. No difference for the evolution of the dynamic susceptibility is observed for the nonfragile system glycerol with respect to fragile glass formers provided that the evolution of the dynamics is studied as a function of the correlation time tau(alpha).

Two glass transitions and secondary relaxations of methyltetrahydrofuran in a binary mixture.

We investigate the molecular dynamics in the binary glass forming system methyltetrahydrofuran (M-THF) and tristyrene. Although the components are miscible in the full concentration and temperature range, two glass transitions can clearly be distinguished in differential scanning calorimetry. We selectively probe the reorientational dynamics of M-THF and tristyrene by means of dielectric spectroscopy and depolarized dynamic light scattering, respectively. While, apart from the observed plasticizer effect, the motion of the larger molecules remains almost unchanged, it is shown that the smaller M-THF molecules take part in both glass transitions. Moreover, below the upper T(g) of the mixture, the remaining mobile M-THF molecules clearly show confinement effects in their relaxation behavior. In order to elucidate the nature of the observed secondary relaxation processes, we first characterize the influence of the methyl group of M-THF on the dynamics in the mixtures by comparing the results obtained so far with the relaxation behavior observed in blends of THF and tristyrene. Finally, we employ (2)H NMR spectroscopy to clarify the nature of the secondary relaxations of THF-d(8) in the latter mixtures and conclude on the basis of the NMR and dielectric results that the high-frequency wing observed in neat M-THF appears as a genuine Johari-Goldstein ß-relaxation in the mixtures, whereas the faster secondary process is due to internal degrees of freedom of the nonrigid THF ring.

The dynamic susceptibility in glass forming molecular liquids: the search for universal relaxation patterns II.

The susceptibility spectra of ten molecular glass formers are completely interpolated by an extension of the generalized gamma distribution of correlation times. The data cover at least 15 decades in frequency and the interpolation includes both alpha peak and excess wing. It is shown that the line shape parameters and the time constant of the alpha relaxation are related to each other. Master curves are identified by a scaling procedure that involves only three parameters, namely, the glass transition temperature T(g), the fragility m, and the excess wing exponent at T(g). This holds independent of whether a further secondary relaxation peak is present or not. Above a crossover temperature T(x) this unique evolution of the line shape parameters breaks down, and a crossover to a simple peak susceptibility without excess wing is observed. Here, the frequency-temperature superposition principle holds in good approximation up to temperatures well above the melting point. It turns out that the crossover coincides with the temperature at which the low-temperature Vogel-Fulcher law starts to fail upon heating. Thus, the so-called Stickel temperature gets a more physical meaning as it marks a qualitative change in the evolution of the susceptibility spectra of glass formers. Moreover, the interrelation of the line shape parameters can explain why the "Nagel scaling" works in some approximation. Our study demonstrates that the excess wing in molecular glass formers is a secondary relaxation, which is linked to the alpha process in a unique way.

Nonresonant dielectric hole burning in neat and binary organic glass formers.

Binary mixtures of the molecular glass former 2-picoline in oligostyrene, in which the dielectric response of 2-picoline exhibits a particularly broad distribution of correlation times, are investigated by nonresonant dielectric hole-burning (NDHB) spectroscopy and the results are compared with NDHB in neat systems, in particular, glycerol. It turns out that in both substance classes spectral selectivity is achieved, which indicates that dynamics is heterogeneous, i.e., slow and fast responses coexist in the material. However, in binary systems the position of the spectral modifications is completely determined by the spectral density of the pump field, and thus shifts linearly with burn frequency as expected, also at pump frequencies around the alpha-relaxation maximum. It is shown that in binary systems the lifetime tau(rec) of the spectral modifications is determined by the burn frequency omega(p) and exceeds its inverse by about one order of magnitude, indicating long-lived dynamic heterogeneity. The data are described in terms of a previously suggested model of dynamically selective heating, which was extended to include intrinsic nonexponential relaxation. It turns out that the spectral broadening in binary mixtures is not only due to pronounced dynamic heterogeneity, but partially also due to intrinsic broadening of the relaxation function.

Beta relaxation versus high frequency wing in the dielectric spectra of a binary molecular glass former.

The binary molecular glass former 2-picoline in tri-styrene is investigated by means of broadband dielectric spectroscopy with the aim of understanding the role of secondary relaxation processes that emerge during the glass transition. It is shown that the "high frequency wing," which is seen in neat picoline, becomes a separate process in the mixture and exhibits all the features of a Johari-Goldstein relaxation. In particular, the previously found relation between activation energy and Tg is recovered. In addition, below Tg the width parameter of this secondary relaxation is shown to be governed by a common temperature dependence, and the time scale is characterized by an isokinetic point. Above Tg pronounced deviations from an Arrhenius behavior are observed.