Experimental Study on the Transport of Light Gas Molecules through Low-Density Polyethylene Films

An original experimental procedure for the study of gas permeation process through thin polymer films is presented. Employing mass spectroscopy techniques, this procedure allows the detection of the permeation flux with a signal-to-noise ratio large enough to obtain accurate measurements of the gas diffusivity also in processes with transient transport conditions lasting for short-interval times (~few seconds). The procedure is validated using as test material a thin low-density polyethylene (LDPE) film: the transport of four test gases with different molecular sizes and condensation properties (CO2, N2, D2, and He) is studied in the 295 to 350 K temperature interval. The CO2 diffusivity values well compare with values previously obtained studying the same LDPE film samples by integral permeation technique measuring the time lag value. Original data on the diffusivity of the He and D2 penetrant molecules are reported: in the examined temperature range, the diffusivity values of these small-size penetrants are in the 10−6 cm2/s range and follow an Arrhenius behavior with temperature. The activation energy values for diffusion are 18.8 ± 0.4 and 10.0 ± 0.4 kJ/mol for D2 and He, respectively

Exploring the membrane-based separation of CO2/CO mixtures for CO2 capture and utilisation processes: Challenges and opportunities

The separation and removal of CO2 from its mixtures with CO2 is gaining increasing interest due to the novel processes in which these two gases are mixed, such as the non-thermal plasma activated reaction of CO2 splitting, a promising CO2 utilisation route that could be performed using renewable energy. The aim of this review is to propose a novel database suitable for membrane scientists to evaluate the feasibility of membrane-based separation processes involving such gas mixture, not included in the original Robeson’s works on the upper bound, nor in later developments. For this reason, we reviewed the data on the permeation, diffusion and sorption of these two gases in different classes of polymers, from polyolefins to polyimides and green polymers, spanning over a wide range of permeability values. Furthermore, we propose an upper bound for this separation, and provide a theoretical explanation for it. The separation mechanism is solubility-driven, and all polymeric membranes inspected in the literature show a CO2-selective behaviour, despite a very limited, or unfavourable, diffusion selectivity for CO2, which is consistent with empirical correlations. Consequently, the observed selectivity values are determined by the solubility-selectivity and are comprised mainly in the range 7–20, in agreement with known empirical correlations between the solubility and the critical temperature of the penetrants. Temperature has a detrimental effect onCO2/CO selectivity, as the activation energy for permeation of CO2 is always lower than that of CO. In general, while the permeability can vary over several orders of magnitude depending on the polymer nature, selectivity mostly ranges between 7 and 20, which makes the trade-off mechanism between permeability and selectivity rather weak in the case of this mixture. Such an effect provides a wider variety of design choices, and makes this separation attractive for polymeric membranes, if carried out at low temperatures and with CO2-philic materials. A preliminary calculation of the separation obtainable with single-stage membrane unit for a binary mixture is carried out for some representative polymers

Polymer rigidification in graphene based nanocomposites: Gas barrier effects and free volume reduction

The gas transport properties of polymer nanocomposite membranes made of Few Layer Graphene nanoplatelets dispersed in amine-modified epoxy resins were studied by gas phase permeation analysis with H2, N2 and CO2. The gas permeability of the nanocomposites decreases with increasing filler content. Filler addition does not change the gas selectivity of the pure epoxy membrane. Positron Annihilation Lifetime Spectroscopy analysis indicates that, by increasing the filler content, the free volume structure does not change but the fractional free volume decreases. Gas transport results were explained by the formation of a constrained polymer region of thickness lif at the filler-matrix interface. The lif parameter was evaluated from the reduction of the fractional free volume of the nanocomposite samples with respect to that of the epoxy matrix. The average value of lif around 20 nm, permits to reproduce quantitatively the experimental data at all examined temperatures, filler concentration and test gas

Hydrogen desorption properties of MgH2/LiAlH4 composites

The hydrogen desorption properties of MgH2-LiAlH4 composites obtained by mechanical milling for different milling times have been investigated by Thermal Desorption Spectroscopy (TDS) and correlated to the sample microstructure and morphology analysed by X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The MgH2-LiAlH4 composites show improved hydrogen desorption properties in comparison with both as-received and ball-milled MgH2. Mixing of MgH2 with small amount of LiAlH4 (5 wt.%) using short mechanical milling (15 min) shifts, in fact, the hydrogen desorption peak to lower temperature than those observed with both as-received and milled MgH2 samples. Longer mixing times of the MgH2-LiAlH4 composites (30 and 60 mm) reduce the catalytic activity of the LiAlH4 additive as revealed by the shift of the hydrogen desorption peak to higher temperatures. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved

Free volumes and gas transport in polymers: Amine-modified epoxy resins as a case study

The CO2 transport process was studied in a series of amine-modified epoxy resins having different cross-linking densities but the same chemical environment for the penetrant molecules. Positron Annihilation Lifetime Spectroscopy (PALS) was used to monitor the free volume structure of the samples and experimentally evaluate their fractional free volume fh(T) and its temperature evolution. The analysis of the free volume hole size distribution showed that all the holes have a size large enough to accommodate the penetrant molecules at temperatures T above the glass transition temperature Tg. The measured gas diffusion constants at T > Tg have been reproduced in the framework of the free volume theory of diffusion using a novel procedure based on the use of fh(T) as an input experimental parameter

Multifunctionality of Reduced Graphene Oxide in Bioderived Polylactide/Poly(Dodecylene Furanoate) Nanocomposite Films

This work reports on the first attempt to prepare bioderived polymer films by blending polylactic acid (PLA) and poly(dodecylene furanoate) (PDoF). This blend, containing 10 wt% PDoF, was filled with reduced graphene oxide (rGO) in variable weight fractions (from 0.25 to 2 phr), and the resulting nanocomposites were characterized to assess their microstructural, thermal, mechanical, optical, electrical, and gas barrier properties. The PLA/PDoF blend resulted as immiscible, and the addition of rGO, which preferentially segregated in the PDoF phase, resulted in smaller (from 2.6 to 1.6 µm) and more irregularly shaped PDoF domains and in a higher PLA/PDoF interfacial interaction, which suggests the role of rGO as a blend compatibilizer. rGO also increased PLA crystallinity, and this phenomenon was more pronounced when PDoF was also present, thus evidencing a synergism between PDoF and rGO in accelerating the crystallization kinetics of PLA. Dynamic mechanical thermal analysis (DMTA) showed that the glass transition of PDoF, observed at approx. 5 °C, shifted to a higher temperature upon rGO addition. The addition of 10 wt% PDoF in PLA increased the strain at break from 5.3% to 13.0% (+145%), and the addition of 0.25 phr of rGO increased the tensile strength from 35.6 MPa to 40.2 MPa (+13%), without significantly modifying the strain at break. Moreover, rGO decreased the electrical resistivity of the films, and the relatively high percolation threshold (between 1 and 2 phr) was probably linked to the low aspect ratio of rGO nanosheets and their preferential distribution inside PDoF domains. PDoF and rGO also modified the optical transparency of PLA, resulting in a continuous decrease in transmittance in the visible/NIR range. Finally, rGO strongly modified the gas barrier properties, with a remarkable decrease in diffusivity and permeability to gases such as O2, N2, and CO2. Overall, the presented results highlighted the positive and sometimes synergistic role of PDoF and rGO in tuning the thermomechanical and functional properties of PLA, with simultaneous enhancement of ductility, crystallization kinetics, and gas barrier performance, and these novel polymer nanocomposites could thus be promising for packaging applications

An Angiopep2-PAPTP Construct Overcomes the Blood-Brain Barrier. New Perspectives against Brain Tumors

A developing family of chemotherapeutics—derived from 5-(4-phenoxybutoxy)psoralen (PAP-1)—target mitochondrial potassium channel mtKv1.3 to selectively induce oxidative stress and death of diseased cells. The key to their effectiveness is the presence of a positively charged triphenylphosphonium group which drives their accumulation in the organelles. These compounds have proven their preclinical worth in murine models of cancers such as melanoma and pancreatic adenocarcinoma. In in vitro experiments they also efficiently killed glioblastoma cells, but in vivo they were powerless against orthotopic glioma because they were completely unable to overcome the blood-brain barrier. In an effort to improve brain delivery we have now coupled one of these promising compounds, PAPTP, to well-known cell-penetrating and brain-targeting peptides TAT48–61 and Angiopep-2. Coupling has been obtained by linking one of the phenyl groups of the triphenylphosphonium to the first amino acid of the peptide via a reversible carbamate ester bond. Both TAT48–61 and Angiopep-2 allowed the delivery of 0.3–0.4 nmoles of construct per gram of brain tissue upon intravenous (i.v.) injection of 5 µmoles/kg bw to mice. This is the first evidence of PAPTP delivery to the brain; the chemical strategy described here opens the possibility to conjugate PAPTP to small peptides in order to fine-tune tissue distribution of this interesting compound