High-Field Electron Paramagnetic Resonance Reveals a Stable Glassy Fraction up to Melting in Semicrystalline Poly(dimethylsiloxane)

The reorientation of the guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. Accurate numerical simulations of the HF-EPR lineshapes evidence that the reorientation times of the spin probes are distributed between the melting temperature Tm and Tm-30 K. The distribution exhibits, in addition to a broad component, a narrow component with low mobility up to the PDMS melting point. It is shown that the temperature dependence of the reorientation time of the spin probes with low mobility is the same of the spin probes in glassy PDMS. The result suggests that the low-mobility fraction is localized in the so-called rigid amorphous fraction

Local Reversible Melting in Semicrystalline Poly(dimethylsiloxane): A High-Field Electron Paramagnetic Resonance Study

The reorientation of the paramagnetic guest 4-methoxy-TEMPO (spin probe) in the disordered fraction of semicrystalline poly(dimethylsiloxane) (PDMS) is investigated by high-field electron paramagnetic resonance (HF-EPR) at 190 and 285 GHz. The distribution of reorientation times is evidenced by accurate numerical simulations of the HF-EPR line shapes above 200 K. The distribution exhibits a bimodal structure with (i) a broad component corresponding to spin probes with fast and intermediate mobility located in the disordered fraction far from the crystallites and (ii) a narrow component corresponding to spin probes with extremely low mobility trapped close to the crystallites in a glassy environment persisting up to the PDMS melting. The spin probe undergoes an exchange process between the trapped and the more mobile fractions which is accounted for by an equilibrium reversible process with standard Gibbs free energy of reaction per spin probe mole Î\u94Gr0 â\u89\u83 4(Î\u94Hm - TÎ\u94Sm), where Î\u94Sm is the equilibrium melting entropy per monomer mole following the absorption of the heat Î\u94Hm. The process is interpreted as signature of reversible tertiary nucleation, occurring at the intersection of crystalline surfaces, thus suggesting surface roughness of the crystal-amorphous interface. It becomes thermodynamically favored at temperatures higher than T â\u88¼ 209 K where the onset of PDMS melting is located according to differential scanning calorimetry

Ionic Liquids as Working Fluids for Heat Storage Applications: Decomposition Behavior of N-Butyl-N-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate

Ionic liquids (ILs) represent promising working fluids to be used in thermal energy storage (TES) technologies thanks to their peculiar properties, such as low volatility, high chemical stability, and high heat capacity. Here, we studied the thermal stability of the IL N-butyl-N-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate ([BmPyrr]FAP), a potential working fluid for TES applications. The IL was heated at 200 degrees C for up to 168 h either in the absence or in contact with steel, copper, and brass plates to simulate the conditions used in TES plants. High-resolution magic angle spinning nuclear magnetic resonance spectroscopy was found to be useful for the identification of the degradation products of both the cation and the anion, thanks to the acquisition of H-1, C-13, P-31, and F-19-based experiments. In addition, elemental analysis was performed on the thermally degraded samples by inductively coupled plasma optical emission spectroscopy and energy dispersive X-ray spectroscopy. Our analysis shows a significant degradation of the FAP anion upon heating for more than 4 h, even in the absence of the metal/alloy plates; on the other hand, the [BmPyrr] cation displays a remarkable stability also when heated in contact with steel and brass

Glassforming Liquids, Amorphous and Semicrystalline Polymers: Exploring their Energy Landscape and Dynamical Heterogeneity by Multi-frequency High-Field EPR

AbstractWe review past and recent work carried out on viscous liquids, amorphous and semicrystalline polymers by multifrequency high-field electron paramagnetic resonance (HF-EPR) facility in Pisa. The emphasis is on the enhanced ability to provide fine details of the reorientation process of the paramagnetic guest, the spin probe, revealing features driving the dynamics of the host system, including the energy-barrier distribution of glassy polymers, the dynamical heterogeneity of semicrystalline polymers, and the dynamical changes occurring at the critical temperature predicted by the ideal mode-coupling theory

Dynamics of poly(vinyl butyral) studied using dielectric spectroscopy and 1H NMR relaxometry.

Dielectric spectroscopy and NMR relaxometry unveiled the PVB segmental dynamics across the glass transition temperature

Studies of Organic Matter in Composting, Vermicomposting, and Anaerobic Digestion by 13C Solid-State NMR Spectroscopy

Composting, vermicomposting, and anaerobic digestion are three commonly applied processes for the transformation of organic waste into valuable products for soil amendment. The application of compost, vermicompost, and digestate to soil requires specific properties, such as maturity and stability, strongly related to the composition of organic matter. 13C solid-state Nuclear Magnetic Resonance (SSNMR) has often been applied to follow the transformation of organic matter during waste treatment processes, as well as to assess the quality of the produced amendments and the effectiveness of the treatments. Thanks to the possibility of associating the 13C chemical shift to different functional groups of biomacromolecules present in the waste feedstocks and in the final products, thorough characterizations of organic matter have been performed exploiting 13C cross-polarization magic angle spinning experiments, and semiquantitative descriptions of the evolution of the different groups during composting, vermicomposting and anaerobic digestion have been reported. Here, these studies are reviewed with the aim of highlighting the potential of the application of 13C SSNMR to these complex materials, as well as the critical issues and perspectives

The Effect of Activation on the Structure of Biochars Prepared from Wood and from Posidonia Oceanica: A Spectroscopic Study

The structure of two biochars and of their activated carbons was investigated by Electron Paramagnetic Resonance, Solid State Nuclear Magnetic Resonance, and Fourier Transform Infrared spectroscopies, together with X-ray diffraction and nitrogen adsorption/desorption isotherm measurements. The biochars were obtained from wood and Posidonia Oceanica by slow pyrolysis up to 600 °C, whereas the activated carbons were prepared from the biochars by impregnation with KOH, heating up to 800 °C. Two different KOH:biochar mass ratios were tested in the case of Posidonia, namely 4:1 and 2:1, while only the 4:1 ratio was used for wood. When the larger ratio was used, activation significantly increased the microporosity of the starting biochar, also creating bottle-neck pores not accessible to water molecules, and induced the formation of larger condensed aromatic networks arranged in interconnected conducting domains. In the case of Posidonia, activation using the 2:1 ratio mainly created mesopores and induced an increase in organic radical content by almost four orders of magnitude. This huge increase was related to the presence of minerals in the starting biochar