Solvent and catalyst free vitrimeric poly(ionic liquid) electrolytes.

Polymer electrolytes (PEs) are a promising alternative to overcome shortcomings of conventional lithium ion batteries (LiBs) and make them safer for users. Introduction of self-healing features in PEs additionally leads to prolonged life-time of LIBs, thus tackling cost and environmental issues. We here present solvent free, self-healable, reprocessable, thermally stable, conductive poly(ionic liquid) (PIL) consisting of pyrrolidinium-based repeating units. PEO-functionalized styrene was used as a co-monomer for improving mechanical properties and introducing pendant OH groups in the polymer backbone to act as a transient crosslinking site for boric acid, leading to the formation of dynamic boronic ester bonds, thus forming a vitrimeric material. Dynamic boronic ester linkages allow reprocessing (at 40 °C), reshaping and self-healing ability of PEs. A series of vitrimeric PILs by varying both monomers ratio and lithium salt (LiTFSI) content was synthesized and characterized. The conductivity reached 10-5 S cm-1 at 50 °C in the optimized composition. Moreover, the PILs rheological properties fit the required melt flow behavior (above 120 °C) for 3D printing via fused deposition modeling (FDM), offering the possibility to design batteries with more complex and diverse architectures.

Observation of low heat capacities for vapor-deposited glasses of indomethacin as determined by AC nanocalorimetry.

Highly stable glass films of indomethacin (IMC) with thicknesses ranging from 75 to 2900 nm were prepared by physical vapor deposition. Alternating current (AC) nanocalorimetry was used to evaluate the heat capacity and kinetic stability of the glasses as a function of thickness. Glasses deposited at a substrate temperature of 0.84T(g) displayed heat capacities that were approximately 19 J/(mol K) (4.5%) lower than glasses deposited at T(g) (315 K) or the ordinary glass prepared by cooling the liquid. This difference in heat capacity was observed over the entire thickness range and is significantly larger than the approximately 2 J/(mol K) (0.3%) difference previously observed between aged and ordinary glasses. The vapor-deposited glasses were isothermally transformed into the supercooled liquid above T(g). Glasses with low heat capacities exhibited high kinetic stability. The transformation time increased by an order of magnitude as the film thickness increased from 75 to 600 nm and was independent of film thickness for the thickest films. We interpret these results to indicate that the transformation of stable glass into supercooled liquid can occur by either a surface-initiated or bulk mechanism. In these experiments, the structural relaxation time of the IMC supercooled liquid was observed to be nearly independent of sample thickness.

Comparing calorimetric and dielectric polarization modes in viscous 2-ethyl-1-hexanol.

Dielectric relaxation and dynamic heat capacity measurements are compared for 2-ethyl-1-hexanol near its glass transition temperature Tg in order to further clarify the origin of the prominent Debye-type loss peak observed in many monohydroxy alcohols and other hydrogen-bonding liquids. While the dielectric spectrum epsilon" displays two distinct polarization processes that are separated by a factor of 2000 in terms of the peak frequency, the heat capacity cp" shows only a single peak. The dielectric process with lower amplitude and higher peak frequency coincides with the calorimetric signal, whereas the large dielectric Debye signal is not associated with calorimetric modes. The authors conclude that the Debye process corresponds to a transition among states which differ in energy only in the case of an external electric field.

Nanophase separation and hindered glass transition in side-chain polymers.

Nanophase separation on length scales of 1-5 nanometres has been reported previously for small-molecule liquids, metallic glasses and also for several semicrystalline, liquid-crystalline and amorphous polymers. Here we show that nanophase separation of incompatible main and side-chain parts is a general phenomenon in amorphous side-chain polymers with long alkyl groups. We conclude from X-ray scattering and relaxation spectroscopy data for higher poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) that alkyl groups of different monomeric units aggregate in the melt and form self-assembled alkyl nanodomains with a typical size of 0.5-2 nm. A comparison with data for other polymer series having alkyl groups reveals that important structural and dynamic aspects are main-chain independent. A polyethylene-like glass transition within the alkyl nanodomains is observed and discussed in the context of a hindered glass transition in self-assembled confinements. This is an interesting link between central questions in glass-transition research and structural aspects in nanophase-separated materials.