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The glass formation and the dipolar reorientational motions in deep eutectic solvents (DESs) are frequently overlooked, despite their crucial role in defining the room-temperature physiochemical properties. To understand the effects of these dynamics on the ionic conductivity and their relation to the mechanical properties of the DES, we conducted broadband dielectric and rheological spectroscopy over a wide temperature range on three well-established carboxylic acid-based natural DESs. These are the eutectic mixtures of choline chloride with oxalic acid (oxaline), malonic acid (maline), and phenylacetic acid (phenylaceline). In all three DESs, we observe signs of a glass transition in the temperature dependence of their dipolar reorientational and structural dynamics, as well as varying degrees of motional decoupling between the different observed dynamics. Maline and oxaline display a breaking of the Walden rule near the glass-transition temperature, while the relation between the dc conductivity and dipolar relaxation time in both maline and phenylaceline is best described by a power law. The glass-forming properties of the investigated systems not only govern the orientational dipolar motions and rheological properties, which are of interest from a fundamental point of view, but they also affect the dc conductivity, even at room temperature, which is of high technical relevance. [ABSTRACT FROM AUTHOR]

Employing dielectric spectroscopy, oscillatory shear rheology, and calorimetry, the present work explores the molecular dynamics of the widely used insecticide imidacloprid above and below its glass transition temperature. In its supercooled liquid regime, the applied techniques yield good agreement regarding the characteristic structural (alpha) relaxation times of this material. In addition, the generalized Gemant–DiMarzio–Bishop model provides a good conversion between the frequency-dependent dielectric and shear mechanical responses in its viscous state, allowing for an assessment of imidacloprid's molecular hydrodynamic radius. In order to characterize the molecular dynamics in its glassy regime, we employ several approaches. These include the application of frequency–temperature superposition (FTS) to its isostructural dielectric and rheological responses as well as use of dielectric and calorimetric physical aging and the Adam–Gibbs–Vogel model. While the latter approach and dielectric FTS provide relaxation times that are close to each other, the other methods predict notably longer times that are closer to those reflecting a complete recovery of ergodicity. This seemingly conflicting dissimilarity demonstrates that the molecular dynamics of glassy imidacloprid strongly depends on its thermal history, with high relevance for the use of this insecticide as an active ingredient in technological applications. [ABSTRACT FROM AUTHOR]

Oscillatory shear rheology has been employed to access the structural rearrangements of deeply supercooled sulfuric acid tetrahydrate (SA4H) and phosphoric acid monohydrate, the latter in protonated (PA1H) and deuterated (PA1D) forms. Their viscoelastic responses are analyzed in relation to their previously investigated electric conductivity. The comparison of the also presently reported dielectric response of deuterated sulfuric acid tetrahydrate (SA4D) and that of its protonated analog SA4H reveals an absence of isotope effects for the charge transport in this hydrate. This finding clearly contrasts with the situation known for PA1H and PA1D. Our analyses also demonstrate that the conductivity relaxation profiles of acid hydrides closely resemble those exhibited by classical ionic electrolytes, even though the charge transport in phosphoric acid hydrates is dominated by proton transfer processes. At variance with this dielectric simplicity, the viscoelastic responses of these materials depend on their structural compositions. While SA4H displays a "simple liquid"-like viscoelastic behavior, the mechanical responses of PA1H and PA1D are more complex, revealing relaxation modes, which are faster than their ubiquitous structural rearrangements. Interestingly, the characteristic rates of these fast mechanical relaxations agree well with the characteristic frequencies of the charge rearrangements probed in the dielectric investigations, suggesting appearance of a proton transfer in mechanical relaxation of phosphoric acid hydrates. These findings open the exciting perspective of exploiting shear rheology to access not only the dynamics of the matrix but also that of the charge carriers in highly viscous decoupled conductors. [ABSTRACT FROM AUTHOR]

The self-diffusion coefficient of viscous liquids is estimated on the basis of a simple analysis of their rheological shear spectra. To this end, the Almond–West approach, previously employed to access single-particle diffusivities in ionic conductors, is generalized for application to molecular dynamics in supercooled liquids. Rheology based estimates, presented for indomethacin, ortho-terphenyl, and trinaphthylbenzene, reveal relatively small, yet systematic differences when compared with diffusivity data directly measured for these highly viscous liquids. These deviations are discussed in terms of mechanical Haven ratios, introduced to quantify the magnitude of collective translational effects that have an impact on the viscous flow. [ABSTRACT FROM AUTHOR]

Combining results from impedance spectroscopy and oscillatory shear rheology, the present work focuses on the relation between the mass and charge flows and on how these are affected by the H-bonding in viscous ionic liquids (ILs). In particular, we compare the relaxational behaviors of the paradigmatic IL 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM-TFSI) and its OH-functionalized counterpart 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (OHEMIM-TFSI). Our results and their analysis demonstrate that the presence of cationic OH-groups bears a strong impact on the overall dynamics of OHEMIM-TFSI, although no signatures of suprastructural relaxation modes could be identified in their dielectric and mechanical responses. To check whether at the origin of this strong variation is the H-bonding or merely the difference between the corresponding cation sizes (controlling both the hydrodynamic volume and the inter-charge distance), the present study includes 1-propyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (PMIM-TFSI), mixtures of EMIM-TFSI and PMIM-TFSI with lithium bis(trifluoromethylsulfonyl)imide (Li-TFSI), and mixtures of OHEMIM-TFSI with PMIM-TFSI. Their investigation clearly reveals that the dynamical changes induced by H-bonding are significantly larger than those that can be attributed to the change in the ion size. Moreover, in the mixtures of OHEMIM-TFSI with PMIM-TFSI, a dilution of the OH-groups leads to strong deviations from ideal mixing behavior, thus highlighting the common phenomenological ground of hydroxy-functionalized ILs and other H-bonded liquids. [ABSTRACT FROM AUTHOR]

Combining experimental results obtained with X-ray scattering and field-gradient nuclear magnetic resonance (NMR) and an assessment of new and previous dielectric and rheology data, our study focuses on the molecular weight (Mw) evolution of local structure and dynamics in a homologous series of covalently bonded ionic liquids. Performed on a family of electrolytes with a tailored degree of ionic decoupling, this study reveals the differences between monomeric and oligomeric melts with respect to their structural organization, mass and charge transport, and molecular diffusion. Our study demonstrates that for the monomeric compound, the broadband conductivity and mechanical spectra reflect the same underlying distribution of activation barriers and that the Random Barrier Model describes fairly well both the ionic and structural relaxation processes in these materials. Moreover, the oligomers with chains comprising ten segments only exhibit both structural and dynamical fingerprints of a genuine polymer. A comparison of conductivity levels estimated using the self-diffusion coefficients probed via NMR and those probed directly with dielectric spectroscopy reveals the emerging of ion correlations which are affecting the macroscopic charge transport in these materials in a chain-length dependent manner. [ABSTRACT FROM AUTHOR]

This work reports on frequency dependent ambient-pressure dielectric measurements of hyperquenched glassy water, ice IV, ice VI, as well as a CO2-filled clathrate hydrate, the latter featuring a chiral water network. The dipolar time scales and the spectral shapes of the loss spectra of these specimens are mapped out and compared with literature data on low-density and high-density amorphous ices as well as on amorphous solid water. There is a trend that the responses of the more highly dense amorphous ices are slightly more dynamically heterogeneous than those of the lower-density amorphous ices. Furthermore, practically all of the amorphous ices, for which broadband dielectric spectra are available, display a curved high-frequency wing. Conversely, the high-frequency flanks of the nominally pure ice crystals including ice V and ice XII can be characterized by an approximate power-law behavior. While the spectral shapes of the nominally pure ices thus yield some hints regarding their amorphicity or crystallinity, a comparison of their time scale appears less distinctive in this respect. In the accessible temperature range, the relaxation times of the crystalline ices are between those of low-density and high-density amorphous ice. Hence, with reference also to previous work, the application of suitable doping currently seems to be the best dielectric spectroscopy approach to distinguish amorphous from crystalline ices. [ABSTRACT FROM AUTHOR]

Monohydroxy alcohols with a large supramolecular Debye-type dielectric process often exhibit a significant decoupling between the Debye mode and the structural relaxation. Using shear rheology, a technique that is sensitive to both processes as well, the current work reveals a widely applicable correlation in terms of the dynamical onset and the viscosity enhancement of the supramolecular shear mode with respect to the structural relaxation. Rheological data from an array of about 50 oligomers, associating polymers, (polymerized) ionic liquids, and aqueous solutions corroborate this correlation which thus appears to be generic to many classes of complex fluids. [ABSTRACT FROM AUTHOR]

The monohydroxy alcohol 2-ethyl-1-hexanol mixed with the halogen-substituted alkyl halides 2-ethyl- 1-hexyl chloride and 2-ethyl-1-hexyl bromide was studied using synchrotron-based x-ray scattering. In the diffraction patterns, an oxygen-related prepeak appears. The concentration dependence of its intensity, shape, and position indicates that the formation of the hydrogen-bonded associates of monohydroxy alcohols is largely hindered by the halogen alkane admixture. Using dielectric spectroscopy and high-resolution rheology on the same liquid mixtures, it is shown that these structural features are correlated with the relaxation mechanisms giving rise to supramolecular low-frequency dynamics. [ABSTRACT FROM AUTHOR]

The Kehler Management System (KMS) is a tool for assessing quality in municipalities. Due to technological advancements, globalisation, greater market dynamics, changing values and demographic change, municipalities find themselves in a complex and dynamic field of tension. The diversity and complexity of these fields of activity and relationship structures continue to increase, making it difficult for municipalities to adapt their processes.

Highly unusual linear-response spectra involving contributions from hydrogen-bonded supramolecular processes and from structural relaxations are found in 4-methyl-3-heptanol mixed with 2-ethyl-1-hexylbromide. Although the mean time scales of the underlying relaxations are separated by more than 3 decades, the overall spectra cannot be decomposed into a sum of these processes. This finding challenges the ubiquitous practice of disentangling susceptibility spectra of Debye liquids by adding suitable subspectra. The spectral shape of the studied viscous mixtures is excellently described using the Williams ansatz, here a necessary approach and not as previously considered merely an alternative to additive analyses. [ABSTRACT FROM AUTHOR]