Relaxation and diffusion of an ionic plasticizer in amorphous poly(vinylpyrrolidone).

The present work focuses on the dynamics of the ionic constituents of 1-propyl-3-methyl-imidazolium-bis-(trifluormethylsulfonyl)-imide (PT), a paradigmatic ionic liquid, as an additive in poly(vinylpyrrolidone) (PVP). Hence, the resulting product can be regarded as a polymer electrolyte as well as an amorphous dispersion. Leveraging dielectric spectroscopy and oscillatory shear rheology, complemented by differential scanning calorimetry, the spectral shapes and the relaxation maps of the supercooled PVP-PT mixtures are accessed in their full compositional range. The study also presents dielectric and shear responses of neat PVP with a molecular weight of 2500 g mol-1. We discuss the plasticizing role of the PT additive and the decoupling between ionic dynamics and segmental relaxation in these mixtures. The extracted relaxation times, steady-state viscosities, and conductivities are employed to estimate the translational diffusivities of the ionic penetrants by means of the Stokes-Einstein, Nernst-Einstein, and Almond-West relations. While some of the estimated diffusivities agree with each other, some do not, pointing to the importance of the chosen hydrodynamic approximations and the type of response considered for the analysis. The present extensive dielectric, rheological, and calorimetric study enables a deeper understanding of relaxation and transport of ionic ingredients in polymers, particularly in the slow-dynamics regime which is difficult to access experimentally by direct-diffusivity probes.

Temperature oscillations provide access to high-order physical aging harmonics of a glass forming melt.

A high-resolution, temperature oscillation-based probe of physical aging in complex systems is introduced. The Fourier analysis of the measured responses allows one to extract high-order, aging-related nonlinearities that are not accessible via traditional temperature-jump and temperature-ramp procedures. To demonstrate the potential of this oscillatory approach, we analyze the periodic time evolution of glycerol's structural relaxation using shear rheology as a vehicle. Thereby, we access up to the sixth harmonic and detect aging fingerprints within a resolution range of three orders of magnitude for temperature amplitudes of up to 4 K. The even harmonics are present since aging is not symmetrical with respect to the direction of temperature change. The high-order aging coefficients obtained for glycerol are described reasonably well within the Tool-Narayanaswamy-Moynihan formalism.

Search for a Grotthuss mechanism through the observation of proton transfer.

The transport of protons is critical in a variety of bio- and electro-chemical processes and technologies. The Grotthuss mechanism is considered to be the most efficient proton transport mechanism, generally implying a transfer of protons between 'chains' of host molecules via elementary reactions within the hydrogen bonds. Although Grotthuss proposed this concept more than 200 years ago, only indirect experimental evidence of the mechanism has been observed. Here we report the first experimental observation of proton transfer between the molecules in pure and 85% aqueous phosphoric acid. Employing dielectric spectroscopy, quasielastic neutron, and light scattering, and ab initio molecular dynamic simulations we determined that protons move by surprisingly short jumps of only ~0.5-0.7 Å, much smaller than the typical ion jump length in ionic liquids. Our analysis confirms the existence of correlations in these proton jumps. However, these correlations actually reduce the conductivity, in contrast to a desirable enhancement, as is usually assumed by a Grotthuss mechanism. Furthermore, our analysis suggests that the expected Grotthuss-like enhancement of conductivity cannot be realized in bulk liquids where ionic correlations always decrease conductivity.

Molecular Dynamics and Diffusion in Amorphous Solid Dispersions Containing Imidacloprid.

The main goal of this study is to develop an experimental toolbox to estimate the self-diffusion coefficient of active ingredients (AI) in single-phase amorphous solid dispersions (ASD) close to the glass transition of the mixture using dielectric spectroscopy (DS) and oscillatory rheology. The proposed methodology is tested for a model system containing the insecticide imidacloprid (IMI) and the copolymer copovidone (PVP/VA) prepared via hot-melt extrusion. For this purpose, reorientational and the viscoelastic structural (α-)relaxation time constants of hot-melt-extruded ASDs were obtained via DS and shear rheology, respectively. These were then utilized to extract the viscosity as well as the fragility index of the dispersions as input parameters to the fractional Stokes-Einstein (F-SE) relation. Furthermore, a modified version of Almond-West (AW) formalism, originally developed to describe charge diffusion in ionic conductors, was exercised on the present model system for the estimation of the AI diffusion coefficients based on shear modulus relaxation times. Our results revealed that, at the calorimetric glass-transition temperature (Tg), the self-diffusion coefficients of the AI in the compositional range from infinite dilution up to 60 wt % IMI content lied in the narrow range of 10-18-10-20 m2 s-1, while the viscosity values of the dispersions at Tg varied between 108 Pa s and 1010 Pa s. In addition, the phase diagram of the IMI-PVP/VA system was determined using the melting point depression method via differential scanning calorimetry (DSC), while mid-infrared (IR) spectroscopy was employed to investigate the intermolecular interactions within the solid dispersions. In this respect, the findings of a modest variation in melting point at different compositions stayed in agreement with the observations of weak hydrogen bonding interactions between the AI and the polymer. Moreover, IR spectroscopy showed the intermolecular IMI-IMI hydrogen bonding to have been considerably suppressed, as a result of the spatial separation of the AI molecules within the ASDs. In summary, this study provides experimental approaches to study diffusivity in ASDs using DS and oscillatory rheology, in addition to contributing to an enhanced understanding of the interactions and phase behavior in these systems.

Characterizing Phase Separation of Amorphous Solid Dispersions Containing Imidacloprid.

Amorphous-Amorphous phase separation (AAPS) is an important phenomenon that can impede the performance of amorphous solid dispersions (ASDs). The purpose of this study was to develop a sensitive approach relying on dielectric spectroscopy (DS) to characterize AAPS in ASDs. This includes detecting AAPS, determining the size of the active ingredient (AI) discrete domains in the phase-separated systems, and accessing the molecular mobility in each phase. Using a model system consisting of the insecticide imidacloprid (IMI) and the polymer polystyrene (PS), the dielectric results were further confirmed by confocal fluorescence microscopy (CFM). The detection of AAPS by DS was accomplished by identifying the decoupled structural (α-)dynamics of the AI and the polymer phase. The α-relaxation times corresponding to each phase correlated reasonably well with those of the pure components, implying nearly complete macroscopic phase separation. Congruent with the DS results, the occurrence of the AAPS was detected by means of CFM, making use of the autofluorescent property of IMI. Oscillatory shear rheology and differential scanning calorimetry (DSC) detected the glass transition of the polymer phase but not that of the AI phase. Furthermore, the otherwise undesired effects of interfacial and electrode polarization, which can appear in DS, were exploited to determine the effective domain size of the discrete AI phase in this work. Here, stereological analysis of CFM images probing the mean diameter of the phase-separated IMI domains directly stayed in reasonably good agreement with the DS-based estimates. The size of phase-separated microclusters showed little variation with AI loading, implying that the ASDs have presumably undergone AAPS upon manufacturing. DSC provided further support to the immiscibility of IMI and PS, as no discernible melting point depression of the corresponding physical mixtures was detected. Moreover, no signatures of strong attractive AI-polymer interactions could be detected by mid-infrared spectroscopy within this ASD system. Finally, dielectric cold crystallization experiments of the pure AI and the 60 wt % dispersion revealed comparable crystallization onset times, hinting at a poor inhibition of the AI crystallization within the ASD. These observations are in harmony with the occurrence of AAPS. In conclusion, our multifaceted experimental approach opens new venues for rationalizing the mechanisms and kinetics of phase separation in amorphous solid dispersions.

Structure-Dynamics Interrelation Governing Charge Transport in Cosolvated Acetonitrile/LiTFSI Solutions.

Concentrated ionic solutions present a potential improvement for liquid electrolytes. However, their conductivity is limited by high viscosities, which can be attenuated via cosolvation. This study employs a series of experiments and molecular dynamics simulations to investigate how different cosolvents influence the local structure and charge transport in concentrated lithium bis(trifluoromethane-sulfonyl)imide (LiTFSI)/acetonitrile solutions. Regardless of whether the cosolvent's dielectric constant is low (for toluene and dichloromethane), moderate (acetone), or high (methanol and water), they preserve the structural and dynamical features of the cosolvent-free precursor. However, the dissimilar effects of each case must be individually interpreted. Toluene and dichloromethane reduce the conductivity by narrowing the distribution of Li+-TFSI- interactions and increasing the activation energies for ionic motions. Methanol and water broaden the distributions of Li+-TFSI- interactions, replace acetonitrile in the Li+ solvation, and favor short-range Li+-Li+ interactions. Still, these cosolvents strongly interact with TFSI-, leading to conductivities lower than that predicted by the Nernst-Einstein relation. Finally, acetone preserves the ion-ion interactions from the cosolvent-free solution but forms large solvation complexes by joining acetonitrile in the Li+ solvation. We demonstrate that cosolvation affects conductivity beyond simply changing viscosity and provide fairly unexplored molecular-scale perspectives regarding structure/transport phenomena relation in concentrated ionic solutions.

Nongeneric structural-relaxation shape of supercooled liquids: Insights from linear and nonlinear experiments on propylene glycol.

Currently, there is a debate whether the structural relaxation of polar liquids is more faithfully reflected (i) by the generically shaped response detected by dynamic light scattering or rather (ii) by the slower, more stretched, system-dependent susceptibility response recorded by dielectric spectroscopy. In this work, nonlinearly induced transients probing structural relaxation reveal that near the glass transition, alternative (ii) is appropriate for propylene glycol. Results from shear rheology and from calorimetry corroborate this finding, underscoring the previously advanced notion (Moch et al., Phys. Rev. Lett. 128, 228001, 2022) that the reorientationally probed structural susceptibility of viscous liquids displays a nongeneric spectral shape.

Predicting Dielectric and Shear-Rheology Properties of Glass-Forming Pharmaceutical Liquids from Each Other: Applications and Limitations.

Acetaminophen, nicotine, and lidocaine hydrochloride were investigated in their deeply supercooled liquid states using oscillatory shear rheology. The mechanical spectra of these drugs are presented in modulus, compliance, as well as fluidity formats. Their frequency profiles can be described via models adapted from the field of charge transport. Inspired by the success of this approach, the Barton-Nakajima-Namikawa relation, best known from the same field, was also tested. When adapted to rheology, this approach interrelates static and dynamic characteristics of viscous flow and was found to work excellently. The temperature dependence of the characteristic shear frequencies was checked against the shoving model, which relates them to the temperature-dependent instantaneous shear modulus and acceptable agreement was found. Combined with shear mechanical literature data on ibuprofen and indomethacin, a modified version of the phenomenological model by Gemant, DiMarzio, and Bishop (GDB) was employed to successfully predict the shape and amplitude of the dielectric spectra for all studied liquids, except for lidocaine hydrochloride. For the latter, the modified GDB model is suggested to aid in mapping out the reorientational part of the dielectric response, while the experimental results are strongly superimposed by ionic conduction phenomena. The reverse transformation, the calculation of rheological spectra based on dielectric ones, is also successfully demonstrated. For the example of acetyl salicylic acid, it is shown how dielectric spectra can be used to even predict rheological ones. The limits of the central parameter governing these mutual transformations, the electroviscoelastic material constant, and indications for its correlation with the dielectric relaxation strength are discussed. For pharmaceuticals characterized by a strong dynamical decoupling of the electrical from the mechanical degrees of freedom, the modified GDB model is not expected to be applicable.

Advances in the study of supercooled water.

In this review, we report recent progress in the field of supercooled water. Due to its uniqueness, water presents numerous anomalies with respect to most simple liquids, showing polyamorphism both in the liquid and in the glassy state. We first describe the thermodynamic scenarios hypothesized for the supercooled region and in particular among them the liquid-liquid critical point scenario that has so far received more experimental evidence. We then review the most recent structural indicators, the two-state model picture of water, and the importance of cooperative effects related to the fact that water is a hydrogen-bonded network liquid. We show throughout the review that water's peculiar properties come into play also when water is in solution, confined, and close to biological molecules. Concerning dynamics, upon mild supercooling water behaves as a fragile glass former following the mode coupling theory, and it turns into a strong glass former upon further cooling. Connections between the slow dynamics and the thermodynamics are discussed. The translational relaxation times of density fluctuations show in fact the fragile-to-strong crossover connected to the thermodynamics arising from the existence of two liquids. When considering also rotations, additional crossovers come to play. Mobility-viscosity decoupling is also discussed in supercooled water and aqueous solutions. Finally, the polyamorphism of glassy water is considered through experimental and simulation results both in bulk and in salty aqueous solutions. Grains and grain boundaries are also discussed.

First- and third-order shear nonlinearities across the structural relaxation peak of the deeply supercooled pharmaceutical liquid indomethacin.

Nonlinear rheological properties of viscous indomethacin are studied in the frequency range of its structural relaxation, that is, in a range so far inaccessible to standard techniques involving medium-amplitude oscillatory shear amplitudes. The first- and third-order nonlinearity parameters thus recorded using a sequence of small and large shear excitations in a time efficient manner are compared with predictions from rheological models. By properly phase cycling the shear amplitudes, build-up and decay transients are recorded. Analogous to electrical-field experiments, these transients yield direct access to the structural relaxation times under linear and nonlinear shearing conditions. To demonstrate the broader applicability of the present approach, transient analyses are also carried out for the glass formers glycerol, ortho-terphenyl, and acetaminophen.

Systematic differences in the relaxation stretching of polar molecular liquids probed by dielectric vs magnetic resonance and photon correlation spectroscopy.

Relaxation spectra of molecular glass formers devoid of secondary relaxation maxima, as measured by dielectric spectroscopy (DS), nuclear magnetic resonance (NMR) relaxometry, photon correlation spectroscopy (PCS), and Fabry-Perot interferometry, are quantitatively compared in terms of the Kohlrausch stretching parameter ßK. For a reliable estimate of ßK, the excess wing contribution has to be included in the spectral analysis. The relaxation stretching probed by PCS and NMR varies only weakly among the liquids (ßK = 0.58 ± 0.06). It is similar to that found in DS, provided that the liquid is sufficiently nonpolar (relaxation strength Δε≲6). For larger strengths, larger ßK DS (narrowed relaxation spectra) are found when compared to those reported from NMR and PCS. Frequency-temperature superposition (FTS) holds for PCS and NMR. This is demonstrated by data scaling and, for the few glass formers for which results are available, by the equivalence of the susceptibilities χPCS ″ωτ∝χNMR ″τ∝χNMR ″ω, i.e., measuring at a constant frequency is equivalent to measuring at a constant temperature or constant correlation time. In this context, a plot of the spin-lattice relaxation rate R1(T) as a function of the spin-spin relaxation rate R2(T) is suggested to reveal the stretching parameter without the need to perform frequency-dependent investigations. Dielectrically, we identify a trend of increasing deviations from FTS with increasing Δε. Depending on the technique and glass former, the relative relaxation strength of the excess wing varies, whereas its exponent appears to be method independent for a given substance. For polar liquids, we discuss possible reasons for the discrepancy between the results from PCS and NMR as compared to those from DS.

Suppression of Orientational Correlations in the Viscous-Liquid State of Hyperquenched Pressure-Densified Glycerol.

Glycerol pressurized to 2 kbar and hyperquenched from the bulk liquid at rates of about -10 000 K/s, has been frozen to an extreme out-of-equilibrium state. As compared to conventionally cooled melts, the resulting material exhibits lower orientational correlations, enabling the observation of a secondary relaxation peak in the ambient-pressure dielectric response. The hyperquenching rather than the pressurizing part of the preparation protocol induces the observed structural changes. These vanish entirely only well above the glass transition temperature of the equilibrium liquid and are evidence for strong similarities between hyperquenched and vapor-deposited glass formers.

Modulation of Cation Diffusion by Reversible Supramolecular Assemblies in Ionic Liquid-Based Nanocomposites.

Ionic liquid (IL) properties, such as high ionic conductivity under ambient conditions combined with nontoxicity and nonflammability, make them important materials for future technologies. Despite high ion conductivity desired for battery applications, cation transport numbers in ILs are not sufficient enough to attain high power density batteries. Thus, developing novel approaches directed toward improvement of cation transport properties is required for the application of ILs in energy-storing devices. In this effort, we used various experimental techniques to demonstrate that the strategy of mixing ILs with ultrasmall (1.8 nm) nanoparticles (NPs) resulted in melt-processable composites with improved transport numbers for cations at room temperature. This significant enhancement in the transport number was attributed to the specific chemistry of NPs exhibiting a weaker cation and stronger anion coordination at ambient temperature. At high temperature, significantly weakened NP-anion associations promoted a liquid-like behavior of composites, highlighting the melt-processability of these composites. These results show that designing a reversible dynamic noncovalent NP-anion association controlled by the temperature may constitute an effective strategy to control ion diffusion. Our studies provide fundamental insights into mechanisms driving the charge transport and offer practical guidance for the design of melt-processable composites with an improved cation transport number under ambient conditions.

Spectral shape simplicity of viscous materials.

A broad survey of viscoelastic data demonstrates that van der Waals, hydrogen-bonded, and ionic liquids, as well as polymeric, inorganic, and metallic melts share a structural relaxation pattern virtually insensitive to their morphological details. This mechanical simplicity is connected with that characterizing the fast reorientation dynamics prevailing in liquids devoid of a distinguishable secondary susceptibility peak. By these means one is able to uncover a generic spectral pattern which rationalizes the recently reported "universality" of relaxation strength vs stretching of the dielectric response of viscous liquids, significantly broadening the framework in which their relaxation behavior is assessed.

Deeply supercooled aqueous LiCl solution studied by frequency-resolved shear rheology.

To characterize the structural relaxation of an aqueous solution of LiCl, frequency-dependent shear rheological experiments are carried out near its glass transition. Analyzed within the fluidity representation, the generic spectral shape that was previously found for a range of different kinds of glass formers is confirmed for the currently studied hydrogen-bonded fluid as well. Furthermore, the validity of the rheological equivalent of the Barton-Nakajima-Namikawa relation is demonstrated for the aqueous LiCl solution. Its mechanical response is compared with that obtained using dielectric spectroscopy, a technique which is sensitive to both the reorientational dynamics of the water molecules and the translational dynamics of the ionic species. The extent to which these electrical polarization processes are coupled to those governing the viscoelastic response is discussed, also in comparison with the behavior of other ion conducting liquids.

Nonlinear electrical and rheological spectroscopies identify structural and supramolecular relaxations in a model peptide.

Supercooled liquid secondary amides display an electrical absorption peak characterized by an almost Debye-like shape, indicative of a close-to-exponential polarization response. This response, believed to be supramolecular in nature, is so enormously intense that the amide's structural process, contributing only a few percent to the total relaxation strength, is hard to resolve reliably using standard dielectric spectroscopy. To overcome this issue, nonlinear dielectric spectroscopy involving field-induced structural recovery and temperature-induced physical aging, was applied near the calorimetric glass transition of a mixture of N-methylformamide and N-ethylacetamide. Without the need to rely on cumbersome deconvolution procedures, it is thus demonstrated that the supramolecular response is by a factor of 6 slower than the structural relaxation. Conversely, in linear rheological experiments only the structural relaxation could be resolved, but not the supramolecular one. However, medium-amplitude oscillatory shear experiments carried out at 160 K do reveal the supramolecular process. Hence, the combination of linear and nonlinear mechanical measurements corroborates the dielectrically uncovered spectral separation of the two processes.

Local and global dynamics of the viscous ion conductors 2Ca(NO3)2-3KNO3 and 2Ca(NO3)2-3RbNO3 probed by 87Rb nuclear magnetic resonance and shear rheology.

The microscopic and macroscopic dynamics of calcium alkali nitrate melts are studied in their supercooled regime by means of shear rheology and nuclear magnetic resonance (NMR). The structural relaxation is probed using shear rheology to access the viscoelastic flow as well as using physical aging experiments. By exploiting the strongly quadrupole-perturbed 87Rb nucleus, the local dynamics is probed on the milliseconds to nanoseconds range using various NMR methods involving central-transition stimulated-echo techniques, line shape analyses, spin relaxations, and second-order dynamic shift effects. The time scales monitored via the local Rb probe are in harmony with the electrical conductivity relaxation times. The low-temperature NMR line shapes agree excellently with those predicted by the Czjzek model. The temperature dependent second-order dynamic frequency shift is described using the imaginary part of the spectral density. It is demonstrated how the latter quantity can be generalized to include effects of correlation time distributions.

Linear and nonlinear shear studies reveal supramolecular responses in supercooled monohydroxy alcohols with faint dielectric signatures.

Monohydroxy alcohols (MAs) with methyl and hydroxyl side groups attached to the same carbon atom in the alkyl backbone can display very weak structural and supramolecular dielectric relaxation processes when probed in the regime of small electrical fields. This can render their separation and assignment difficult in the pure liquids. When mixing with bromoalkanes, a faint Debye-like process can be resolved dielectrically for 4-methyl-4-heptanol. To achieve a separation of structural and supramolecular processes in pure 4-methyl-4-heptanol and 3-methyl-3-heptanol, mechanical experiments are carried out in the linear-response regime as well as using medium-angle oscillatory shear amplitudes. It is demonstrated that first-order and third-order nonlinear mechanical effects allow for a clear identification of supramolecular viscoelastic modes even for alcohols in which they leave only a weak signature in the linear-response shear modulus. Additionally, the nonlinear rheological behavior of 2-ethyl-1-hexanol is studied, revealing that its linearly detected terminal mode does not coincide with that revealed beyond the linear-response regime. This finding contrasts with those for the other MAs studied in this work.

Coexistence of two structural relaxation processes in monohydroxy alcohol-alkyl halogen mixtures: Dielectric and rheological studies.

Evidence for the existence of two glass transitions is found in binary mixtures of monohydroxy alcohols with an aprotic alkyl halide by means of dielectric spectroscopy and, markedly, also shear rheology. In the mechanical data, an enormous separation of two components becomes obvious for suitable compositions. The observation of bimodal motional heterogeneity is possible despite the fact that the glass transition temperatures of these substances differ by only 40 K. Obviously, the hydrogen-bond driven formation of supramolecular structures in one of the mixture components facilitates the emergence of dynamic contrast which for other binary liquids was so far only observed in the presence of much larger glass transition temperature differences.

Transient Nonlinear Response of Dynamically Decoupled Ionic Conductors.

The present study demonstrates that large electric fields progressively enhance the conductivity of ionic systems up to timescales corresponding to those on which their structural rearrangements take place. Yet, in many ionic materials, some regarded as candidates for electrical energy storage applications, the structural relaxation process can be tremendously slower than (or highly decoupled from) the charge fluctuations. Consequently, nonlinear dielectric spectroscopy may be employed to access rheological information in dynamically decoupled ionic conductors, whereas the combination of large electric power density and good mechanical stability, both technologically highly desired, imposes specific experimental constraints to reliably determine the steady-state conductivity of such materials.