Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

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The mechanism of charge transport in the imidazolium-based ionic liquid 1,3-dimethylimidazolium dimethylphosphate is analyzed by combining broadband dielectric spectroscopy (BDS) and pulsed field gradient nuclear magnetic resonance (PFG NMR). The dielectric spectra are dominated-on the low-frequency side-by electrode polarization effects while, for higher frequencies, charge transport in a disordered matrix is the underlying physical mechanism. Using the Einstein and Einstein-Smoluchowski equations enables one to determine-in excellent agreement with direct measurements by PFG NMR-the diffusion coefficient of the charge carriers. By that, it becomes possible to extract from the dielectric spectra separately the number density and the mobilities of the charge carriers and the type of their thermal activation. It is shown that the observed Vogel-Fulcher-Tammann (VFT) dependence of the dc conductivity can be traced back to a similar temperature dependence of the mobility while for the number density an Arrhenius-type thermal activation is found. Extrapolating the latter to room temperature indicates that nearly all charge carriers are participating in the conduction process.

Broadband dielectric spectroscopy (BDS), spectroscopic vis-ellipsometry (SE), X-ray reflectometry (XRR), and alternating current (ACC) as well as differential scanning calorimetry (DSC) are combined to study glassy dynamics and the glass transition in nanometric thin (≥5 nm) layers of polystyrene (PS) having widely varying molecular weights (27 500−8 090 000 g/mol). For the dielectric measurements two sample geometries are employed, the common technique using evaporated electrodes and a recently developed approach taking advantage of nanostructures as spacers. All applied methods deliver the concurring result that deviations from glassy dynamics and from the glass transition of the bulk do not exceed margins of ±3 K independent of the layer thickness and the molecular weight of the polymer under study. Our findings are discussed in the context of the highly controversial literature and prove that an appropriate sample preparation is of paramount importance.

International audienceNanoscale patterning of piezoelectric and ferroelectric polymers, such as polyvinylidene fluoride (PVdF) and its copolymers with trifluoroethylene (PVdF-TrFE), is increasingly important in organic electronics, memory, and sensing. The nanoscale processing of polymers can lead to materials behavior that is strikingly different from the bulk because of confinement effects. Here we report the effects of confinement of PVdF-TrFE melt-wetted in porous templates of varying pore diameter. PVdF-TrFE is particularly interesting because it possesses a solid-state Curie transition, where both ferro and nonferroelectric phases crystallize into a paraelectric phase. Using modulated differential scanning calorimetry (MDSC), X-ray diffraction (XRD), and broadband dielectric spectroscopy (BDS), we demonstrate that confined PVdF-TrFE crystallizes into an oriented ferroelectric beta phase. Both melting and crystallization temperatures decrease with decreasing pore diameter, and the Curie temperature is weakly affected. Results imply that nanoconfinement enhances the formation and orientation of the ferroelectric beta phase and could potentially enhance ferroelectricty and piezoelectricity in nanoscale PVdF-TrFE features

Broadband dielectric and terahertz spectroscopy (10(-2)-10(+12) Hz) are combined with pulsed field gradient nuclear magnetic resonance (PFG-NMR) to explore charge transport and translational diffusion in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid. The dielectric spectra are interpreted as superposition of high-frequency relaxation processes associated with dipolar librations and a conductivity contribution. The latter originates from hopping of charge carriers on a random spatially varying potential landscape and quantitatively fits the observed frequency and temperature dependence of the spectra. A further analysis delivers the hopping rate and enables one to deduce--using the Einstein-Smoluchowski equation--the translational diffusion coefficient of the charge carriers in quantitative agreement with PFG-NMR measurements. By that, the mobility is determined and separated from the charge carrier density; for the former, a Vogel-Fulcher-Tammann and for the latter, an Arrhenius temperature dependence is obtained. There is no indication of a mode arising from the reorientation of stable ion pairs.

The characteristic frequencies of electrode polarization and of interfacial polarization effects in dielectric spectra of ionic liquids and of polymer bi-layers are determined and systematically analyzed, based on dielectric measurements by means of broadband dielectric spectroscopy, numerical simulations, and analytical calculations. It is shown that, to a large extent, identical scaling laws can be derived for these two dielectric phenomena taking place at external and internal interfaces. Surprisingly, a fundamentally different behavior concerning the interrelation between the characteristic frequencies is found. This brings direct evidence that different manifestations of the phenomenon of electrical polarization can be discriminated by examining the inter-relation governing their characteristic frequencies, which can be of significant importance in disseminating the nature of different contributions appearing in the dielectric spectra of complex materials. Based on our analysis, we derive a new formula, valid for both electrode polarization and interfacial polarization effects, that allows one to determine the conductivity value from the frequency position of the Maxwell-Wagner-Sillars peak. An excellent agreement between experiment and calculations is obtained. The formula can be used, furthermore, to estimate the thickness of the interfacial layers formed due to electrode polarization effects. Values in the order of several nanometers, increasing with decreasing temperature, are reported.

The molecular dynamics in thin polymer layers having a free upper interface is investigated by means of Broadband Dielectric Spectroscopy and AC-calorimetry. Down to film thicknesses of ∼10 nm no shifts in the average relaxation time and no broadening of the dynamic glass transition are detected for polystyrene, poly(methyl methacrylate), poly(vinyl acetate), poly(γ-benzyl-l-glutamate) and poly(2-vinyl pyridine). This experimental finding restricts to a few nanometers the length-scale of a possible alteration of the polymer mobility in the vicinity of free interfaces.