Maria Giovanna Pastore Carbone

Raman Line Imaging of Poly(ε-caprolactone)/Carbon Dioxide Solutions at High Pressures: A Combined Experimental and Computational Study for Interpreting Intermolecular Interactions and Free-Volume Effects

In the present study, a Raman line-imaging setup was employed to monitor in situ the CO2 sorption at elevated pressures (from 0.62 to 7.10 MPa) in molten PCL. The method allowed the quantitative measurement of gas concentration in both the time-resolved and the space-resolved modes. The combined experimental and theoretical approach allowed a molecular level characterization of the system. The dissolved CO2 was found to occupy a volume essentially coincident with its van der Waals volume and the estimated partial molar volume of the probe did not change with pressure. Lewis acid-Lewis base interactions with the PCL carbonyls was confirmed to be the main interaction mechanism. The geometry of the supramolecular complex and the preferential interaction site were controlled more by steric than electronic effects. On the basis of the indications emerging from Raman spectroscopy, an equation of state thermodynamic model for the PCL-CO2 system, based upon a compressible lattice fluid theory endowed with specific interactions, has been tailored to account for the interaction types detected spectroscopically. The predictions of the thermodynamic model in terms of molar volume of solution have been compared with available volumetric measurements while predictions for CO2 partial molar volume have been compared with the values estimated on the basis of Raman spectroscopy.

3-Arm star pyrene-functional PMMAs for efficient exfoliation of graphite in chloroform: fabrication of graphene-reinforced fibrous veils

3-Arm PMMAs end-functionalized by pyrene were designed as dispersing/stabilizing agents for the liquid-phase exfoliation of graphite in low-boiling point solvents like chloroform. The synthetic procedure comprised ARGET ATRP controlled polymerization, click chemistry and the quaternization reaction of triazole, ensuring tailor-made, well-defined pyrene-functional star PMMAs. Among a series of different pyrene-functional macromolecular topologies, the (PMMA-py2)3 proved the most efficient exfoliation agent giving relatively high graphene concentration (0.36 mg ml-1) at exceptionally low polymer/graphite mass ratio (mP/mGF = 0.003) and short sonication time (3 h). A 5-cycle iterative procedure relying on the redispersion of the sediment was developed yielding CG = 1.29 mg ml-1 with 14.8% exfoliation yield, under the favorable conditions of 10.5 h total shear mixing/tip sonication time and overall mP/mGF ratio as low as 0.15. In parallel, all-atom molecular dynamics simulations were conducted which helped understand the mechanism by which pyrene-functional macromolecular topologies act as efficient dispersing agents of graphene. Finally the G@(PMMA-Py)3 hybrids were well dispersed into the PMMA matrix by electrospinning to fabricate graphene-based nanocomposite fibrous veils. These graphene/polymer nanocomposites exhibited enhanced stiffness and strength by a factor of 4.4 with 1.5 wt% graphene hybrids as nanofillers.

Easy-to-fill asymmetric polymeric micro-reservoirs

In this work, we demonstrate the feasibility of micrometric asymmetric reservoirs made of thermoplastic polymers by using the gas foaming method, which has been recently introduced, and consists in forming bubbles in micro- or nano-metric bulk particles as is done with carbonated drinks. As this simplicity anticipates, this represents a breakthrough in the area of micro- and nanoparticles as it responds to the needs of: (i) breaking the symmetry of commonly available systems, (ii) filling the particles with a multitude of host molecules and solutions, (iii) having different shapes, (iv) having a wide range of particle dimensions, (v) having particles made of a wide range of materials. Here we report the achievement of micrometric spherical particles and of micrometric ellipsoidal particles with eccentric holes, filled with crystal violet or with quantum dots as model host molecules. Raman spectroscopy and optical and electron imaging are utilized to verify the effectiveness of the method. This study should open up the use of micro- and nano-metric reservoirs in a multitude of research areas, from biomedicine and pharmacology, to electronics, energy and optics.

Anomalous swelling of molten PCL/scCO2 solutions

The swelling behavior of molten poly(e-caprolactone) in contact with carbon dioxide has been analyzed by using the pendant drop method. At subcritical pressures, the swelling kinetics of the polymer-gas solution follow the typical Fickian diffusion behavior, the volume approaching an equilibrium value after the initial transient. In supercritical conditions, after the first transient, the volume of the solution does not approach an equilibrium value but still, slowly increases. Raman experiments have suggested that this anomalous time-dependent swelling in scCO2 could be due or to slow, secondary diffusion, or to polymer dissolution in scCO2.

PS foams at high pressure drop rates

In this paper, we report data on PS foamed at 100 °C after CO2 saturation at 10 MPa in a new physical foaming batch that achieves pressure drop rates up to 120 MPa/s. Results show how average cell size of the foam nicely fit a linear behavior with the pressure drop rate in a double logarithmic plot. Furthermore, foam density initially decreases with the pressure drop rate, attaining a constant value at pressure drop rates higher than 40 MPa/s. Interestingly, furthermore, we observed that the shape of the pressure release curve has a large effect on the final foam morphology, as observed in tests in which the maximum pressure release rate was kept constant but the shape of the curve changed. These results allow for a fine tuning of the foam density and morphology for specific applications.