Francesco Trequattrini

The present research article deals with the thermal degradation study of epoxy resins filled with hybrid nanostructured forms of carbon under oxidative conditions. In particular, the formulated polymer composites (denoted as HYB_0.1%_CNTs:GNs and HYB_0.5%_CNTs:GNs, respectively) consist of two kinds of fillers, namely multi-walled carbon nanotubes (CNTs) and graphene nanosheets (GNs), mixed together with two different total mass amounts: 0.1 and 0.5%. In both kinds of nanocomposites, three different CNT:GN mixing ratios were considered (5:1, 1:1, and 1:5, respectively), thus providing a total of six hybrid samples. The thermal behavior of these samples was studied by simultaneous thermogravimetry and differential thermal analysis (TG/DTA) under flowing air, and two processes took place in distinct temperature ranges. In each step, about 50% of mass loss is detected with an exothermic effect in the corresponding DTA curve, with the second one accompanied by an intense heat release. The kinetic analysis of the two-stage oxidative thermal degradation was investigated using a model-free isoconversional approach. A non-Arrhenian behavior of the temperature function k(T) was assumed, and lifetime prediction was estimated at temperatures close to those of the possible applications. Isoconversional analysis shows nearly constant activation energies for all composites except HYB_0.1%_5:1 (from 142 to 96 kJ·mol⁻¹), while lifetime predictions indicate that thermal stability increases with graphene content at 0.1% loading (HYB_0.1%_1:5) and with CNT content at 0.5% loading (HYB_0.5%_5:1), with uncertainties below 7%. Finally, because of the π–π bond interactions between the CNTs and the GNs dispersed in the epoxy resin matrix, an effective and remarkable electrical performance was found and a correlation with both electrical and morphological properties was established. In this regard, Tunneling Atomic Force Microscopy (TUNA) proved to be particularly powerful in allowing the simultaneous mapping of topography and localized conductive networks with exceptional sensitivity to nanofiller dispersion, such as CNTs and GNs. DC conductivity increased by up to nine orders of magnitude at 0.1 wt% hybrid loading (up to 3.73 × 10⁻⁴ S/m vs. 1.06 × 10⁻¹³ S/m for CNT-only), with nanoscale TUNA currents (−1.9 to 4.5 pA) mirroring macroscopic trends, while at 0.5 wt% all hybrids reached 10⁻² S/m, indicating reduced synergy once a fully developed conductive network is established.

The vapor pressures, p_v, of three ionic compounds used as starting materials of deep eutectic systems, namely, tetrabutylammonium bromide (TBA-Br), tetrabutylammonium trifluoromethanesulfonate (TBA-TFO), and tetrabutylammonium bis(trifluoromethanesulfonyl)imide (TBA-NTF2), were measured using isothermal thermogravimetry. TBA-Br displays large values of p_v, reaching ≈700 Pa at 170 °C. TBA-NTF2 is the less volatile liquid, with a vapor pressure of ≈1 Pa at 240 °C, while TBA-TFO has a slightly higher value of p_v, of about 3 Pa at the same temperature. The values of p_v for the NTF2-containing ionic compound are comparable to those of ionic liquids containing the same anion. The obtained mean vaporization enthalpy, ΔH_vap, for TBA-Br and TBA-TFO (≈170 kJ mol⁻¹) is higher than for TBA-NTF2 (≈145 kJ mol⁻¹). The obtained vaporization enthalpy values fall within the typical range observed for ionic liquids.

Mixed systems based on ionic liquids are promising innovative solvents due to their properties, which are strictly connected to the interactions that arise among the components. The present work investigates the intermolecular interactions of a mixed choline acetate and maleic acid system and their modifications with increasing acid content. MM/DFT calculations provided indications about the possible geometric configurations of the systems while Non-Covalent Interaction analysis was useful to describe and distinguish secondary interactions. The number of available configurations decreases at high acid concentration. Moreover, intramolecular hydrogen bonding was observed in all configurations except that in the most stable one of the lowest acid content mixture. Concomitantly, far-infrared spectroscopy was used to investigate intermolecular interactions and provided support to the computational results.

For this article, the interaction of tetrabutylammonium trifluoromethanesulfonate (TBATFO) with either fumaric (FUM) or maleic (MAL) acid has been investigated. These acids are isomers and can be considered the trans and cis configurations of the same molecular geometry. When TBATFO is mixed with FUM, an eutectic point is obtained for a relative composition of 90-10 (molar ratio), with a melting point of ≈90 °C. If maleic acid is mixed with TBATFO, one obtains an inhomogeneous phase with the retention of a solid portion immersed in a liquid phase, even above 90 °C. DFT calculations helped to model the interaction between the components. It is suggested herein that TBATFO interacts more strongly with FUM than with MAL, due to possible interactions in two different sites for hydrogen bonding (HB) in FUM. In MAL, one of the HB sites is instead retained in the intramolecular interactions; therefore, fewer sites are available for intermolecular interactions. Infrared spectroscopy measurements have confirmed this scenario, in which the hydrogen bonds of the acid molecules are replaced by HB between the acid and the ionic couple: for both kinds of mixtures, the vibration region of the OH bonds is strongly affected by mixing. However, in the case of FUM, the vibrations of the SO₃ group of the TFO anion are displaced, while they remain in practically the same frequency position in the case of MAL.

The hydrogen/deuterium sorption properties of Ni₃₃Ti₃₉Nb₂₈ synthesized by the vacuum induction melting technique were measured between 400 and 495 °C for pressure lower than 3 bar. The Sieverts law is valid up to H(D)/M < 0.2 in its ideal form; the absolute values of the hydrogenation/deuteration enthalpy are ΔH(H₂) = 85 ± 5 kJ/mol and ΔH(D₂) = 84 ± 4 kJ/mol. From the kinetics of absorption, the diffusion coefficient was derived, and an Arrhenius dependence from the temperature was obtained, with E_a,d = 12 ± 1 kJ/mol for both hydrogen isotopes. The values of the alloy permeability, obtained by combining the solubility and the diffusion coefficient, were of the order of 10⁻⁹ mol m⁻¹ s⁻¹ Pa^−0.5, a value which is one order of magnitude lower than that of Ni₄₁Ti₄₂Nb₁₇, until now the best Ni-Ti-Nb alloy for hydrogen purification. In view of the simplicity of the technique here proposed to calculate the permeability, this method could be used for the preliminary screening of new alloys.

Amorphous SiO₂ thin films are one of the two components of the highly reflective mirror coatings of gravitational-wave detectors. For this study, layers of amorphous SiO₂ on crystalline Si substrates were produced by ion-beam sputtering (IBS), using accelerated neutralized argon ions as sputtering particles, as is the case for the actual mirror coatings of gravitational-wave detectors. The aim of this study is to investigate the possible presence of various defects in the materials in order to improve the coating quality. We provide evidence that, due to the synthesis method, about 0.2 wt.% of Ar is present in the coatings, and it can be released by means of thermal treatments, starting around 400 °C. The time and temperature to obtain the total release of Ar increases with the coating thickness; for a thickness of 100 nm, all argon is released below 600 °C, while an isotherm of one hour at 900 °C is necessary for a coating 5 μm thick. Besides the Ar atoms left from the synthesis, other defects, such as Si clusters and silicon dangling bonds, are present in the coatings. The concentration of both of them is strongly reduced by thermal treatments either in vacuum or in air. The overall thickness of the coating is slightly increased after thermal treatments, as witnessed by the change of the period of interference fringes.

Novel ionic liquid (IL) electrolytes based on the asymmetric (fluoromethylsulfonyl)(trifluoromethylsulfonyl)imide (FTFSI)⁻ anion, combined with the N-trimethyl-N-butyl-ammonium (N1114)⁺ and N,N-diethyl-N-methyl-N(2-methoxyethyl)-ammonium (N122(2O1))⁺ cations, were successfully synthesized and investigated in terms of thermal, vibrational and electrochemical properties. Thermogravimetric measurements revealed that the ionic liquids are stable up to 300 °C (2% mass loss). Differential scanning calorimetry measurements evidenced no phase transition down to −90 °C, suggesting a transition towards a glass state at lower temperatures. Infrared spectroscopy measurements, for the first time performed on ILs containing FTFSI, could not detect any crystallization down to −140 °C. The frequency of the main absorption bands of the ILs are in good agreement with DFT calculations. The FTFSI ionic liquid electrolytes, containing 20% mol of LiTFSI, show no solid-liquid phase transition due to the asymmetry of the FTFSI⁻ anion, increasing the −10 °C conductivity up to 10⁻⁴ S cm⁻¹. These interesting ion transport properties remarkably extend the operative temperature range down to low temperatures. The FTFSI electrolytes exhibit remarkable electrochemical stability up to 4.8 V, this making them appealing for realizing safer and highly reliable lithium battery systems operating at high voltages.