Silvia Trabattoni

Ultrasound-Assisted Pullulan/Montmorillonite Bionanocomposite Coating with High Oxygen Barrier Properties

In this paper, the preparation and characterization of oxygen barrier pullulan sodium montmorillonite (Na(+)-MMT) nanocomposite coatings are presented for the first time. Full exfoliation of platelets during preparation of the coating water dispersions was mediated by ultrasonic treatment, which turned out to be a pivotal factor in the oxygen barrier performance of the final material even at high relative humidity (RH) conditions [oxygen permeability coefficients ~1.43 ± 0.39 and 258.05 ± 13.78 mL·μm·m(-2)·(24 h)(-1)·atm(-1) at 23 °C and 0% RH and 70% RH, respectively]. At the micro- and nanoscale, the reasons are discussed. The final morphology of the coatings revealed that clay lamellae were stacked on top of one another, probably due to the forced confinement of the platelets within the coating thickness after solvent evaporation. This was also confirmed by modeling the experimental oxygen permeability data with the well-known Nielsen and Cussler permeation theoretical models, which suggested a reasonable aspect ratio (α) of ~100. Electron microscopic analyses also disclosed a peculiar cell-like arrangement of the platelets. The stacking of the clay lamellae and the cell-like arrangement create the excellent oxygen barrier properties. Finally, we demonstrated that the slight haze increase in the bionanocomposite coating materials arising from the addition of the clays depends on the clay concentration but not so much on the sonication time, due to the balance of opposite effects after sonication (an increase in the number of scattering centers but a reduction in their size).

Polysaccharide-assisted rapid exfoliation of graphite platelets into high quality water-dispersible graphene sheets

Ultrasound exfoliation of graphite with the assistance of three polysaccharides (nonionic pullulan, cationic chitosan, and anionic alginate) was investigated in this work. The effects of polymer type, initial concentration of graphite, and ultrasonication period on the graphene yield and quality were compared. Under a sonotrode-type ultrasonication treatment for 30 min, graphene aqueous dispersions with concentrations of up to 2.3 mg ml−1 in pullulan solutions and 5.5 mg ml−1 in chitosan solutions were achieved. The obtained graphene nanosheets were characterized as low-defect mono-layer, bi-layer, and few-layer (<5), and formed stable dispersions in water for up to 6 months. The adsorption of pullulan and chitosan biopolymers on the graphene surface as determined by TGA technique was approximately 2.5 wt% and 8.5 wt%, respectively, which accounts for the dispersibility and stability of the graphene sheets in water. Findings arising from this work suggest that pullulan and chitosan are more effective in exfoliating graphite into graphene than alginate due to the different surface free energy and thermodynamic affinity. The polysaccharide-assisted aqueous-exfoliation approach enables the production of water-dispersible graphene with high quality and large quantity, thus providing an industrially scalable route for new potential applications of graphene-based nanocomposites, e.g. in the food packaging industry.

Surface properties and wear performances of siloxane-hydrogel contact lenses.

The low surface roughness of disposable contact lenses made of a new siloxane-hydrogel loaded with hyaluronic acid is reported, as studied by atomic force microscopy (AFM). Before the wear, the surface is characterized by out-of-plane and sharp structures, with maximum height of about 10 nm. After a wear of 8 h, evidence of two typical morphologies is provided and discussed. One morphology (sharp type) has a similar aspect as the unworn lenses with a slight increase in both the height and the number of the sharp peaks. The other morphology (smooth type) is characterized by troughs and bumpy structures. Wettability and clinical performances are also discussed, the latter deduced by the ocular-surface-disease index (OSDI). The main finding arising from this work is the indication of correlation between the change of the OSDI before and after wear and the lens surface characteristics obtained by AFM.

Exceptional oxygen barrier performance of pullulan nanocomposites with ultra-low loading of graphene oxide

Polymer nanocomposites are increasingly important in food packaging sectors. Biopolymer pullulan is promising in manufacturing packaging films or coatings due to its excellent optical clarity, mechanical strength, and high water-solubility as compared to other biopolymers. This work aims to enhance its oxygen barrier properties and overcome its intrinsic brittleness by utilizing two-dimensional planar graphene oxide (GO) nanoplatelets. It has been found that the addition of only 0.2 wt% of GO enhanced the tensile strength, Youngs modulus, and elongation at break of pullulan films by about 40, 44 and 52%, respectively. The light transmittance at 550 nm of the pullulan/GO films was 92.3% and haze values were within 3.0% threshold, which meets the general requirement for food packaging materials. In particular, the oxygen permeability coefficient of pullulan was reduced from 6337 to 2614 mL μm m(-2) (24 h(-1)) atm(-1) with as low as 0.05 wt% of GO loading and further to 1357 mL μm m(-2) (24 h(-1)) atm(-1) when GO concentration reached 0.3 wt%. The simultaneous improvement of the mechanical and oxygen barrier properties of pullulan was ascribed to the homogeneous distribution and prevalent unidirectional alignment of GO nanosheets, as determined from the characterization and theoretical modelling results. The exceptional oxygen barrier properties of pullulan/GO nanocomposites with enhanced mechanical flexibility and good optical clarity will add new values to high performance food packaging materials.

Solid State Organic X-Ray Detectors Based on Rubrene Single Crystals

In this work we report the results on the investigation of rubrene single crystals as solid state direct ionizing radiation detectors. With the aim to understand how electrical properties, and in particular a large charge carrier mobility, affect the radiation detection process in organic semiconducting single crystals, we compare the detection performance of rubrene-based devices with those of 1,5-dinitronaphthalene (DNN)-based ones. DNN has been recently proven to be a stable and reliable X-ray direct detector, operating at very low voltages, in air and at room temperature, with a carrier mobility values about two orders of magnitude lower than rubrene. We demonstrate here that the large charge carrier mobility of rubrene crystals does not result in a better X-rays detection performance. In fact, rubrene devices are shown to be less performing than DNN as detectors, with lower sensitivity to X-rays, poorer stability and reproducibility, and longer rise and decay times of the signal.

Morphological Properties of Siloxane-Hydrogel Contact Lens Surfaces

ABSTRACT Purpose: The aim of this study was to quantitatively characterize the micromorphology of contact lens (CL) surfaces using atomic force microscopy (AFM) and multifractal analysis.Materials and Methods: AFM and multifractal analysis were used to characterize the topography of new and worn siloxane-hydrogel CLs made of Filcon V (I FDA group). CL surface roughness was studied by AFM in intermittent-contact mode, in air, on square areas of 25 and 100 μm2, by using a Nanoscope V MultiMode (Bruker). Detailed surface characterization of the surface topography was obtained using statistical parameters of 3-D (three-dimensional) surface roughness, in accordance with ISO 25178-2: 2012.Results: Before wear, the surface was found to be characterized by out-of-plane and sharp structures, whilst after a wear of 8 h, two typical morphologies were observed. One morphology (sharp type) has a similar aspect as the unworn CLs and the other morphology (smooth type) is characterized by troughs and bumpy structures. The analysis of the AFM images revealed a multifractal geometry. The generalized dimension Dq and the singularity spectrum f(α) provided quantitative values that characterize the local scale properties of CL surface geometry at nanometer scale.Conclusions: Surface statistical parameters deduced by multifractal analysis can be used to assess the CL micromorphology and can be used by manufacturers in developing CLs with improved surface characteristics. These parameters can also be used in understanding the tribological interactions of the back surface of the CL with the corneal surface and the front surface of the CL with the under-surface of the eyelid (friction, wear, and micro-elastohydrodynamic lubrication at a nanometer scale).

Graphene Oxide Bionanocomposite Coatings with High Oxygen Barrier Properties

In this work, we present the development of bionanocomposite coatings on poly(ethylene terephthalate) (PET) with outstanding oxygen barrier properties. Pullulan and graphene oxide (GO) were used as main polymer phase and nanobuilding block (NBB), respectively. The oxygen barrier performance was investigated at different filler volume fractions (ϕ) and as a function of different relative humidity (RH) values. Noticeably, the impermeable nature of GO was reflected under dry conditions, in which an oxygen transmission rate (OTR, mL·m−2·24 h−1) value below the detection limit of the instrument (0.01 mL·m−2·24 h−1) was recorded, even for ϕ as low as 0.0004. A dramatic increase of the OTR values occurred in humid conditions, such that the barrier performance was totally lost at 90% RH (the OTR of coated PET films was equal to the OTR of bare PET films). Modelling of the experimental OTR data by Cussler’s model suggested that the spatial ordering of GO sheets within the main pullulan phase was perturbed because of RH fluctuations. In spite of the presence of the filler, all the formulations allowed the obtainment of final materials with haze values below 3%, the only exception being the formulation with the highest loading of GO (ϕ ≈ 0.03). The mechanisms underlying the experimental observations are discussed.

Transparent Pullulan/Mica Nanocomposite Coatings with Outstanding Oxygen Barrier Properties

This study presents a new bionanocomposite coating on poly(ethylene terephthalate) (PET) made of pullulan and synthetic mica. Mica nanolayers have a very high aspect ratio (α), at levels much greater than that of conventional exfoliated clay layers (e.g., montmorillonite). A very small amount of mica (0.02 wt %, which is ϕ ≈ 0.00008) in pullulan coatings dramatically improved the oxygen barrier performance of the nanocomposite films under dry conditions, however, this performance was partly lost as the environmental relative humidity (RH) increased. This outcome was explained in terms of the perturbation of the spatial ordering of mica sheets within the main pullulan phase, because of RH fluctuations. This was confirmed by modelling of the experimental oxygen transmission rate (OTR) data according to Cussler’s model. The presence of the synthetic nanobuilding block (NBB) led to a decrease in both static and kinetic coefficients of friction, compared with neat PET (≈12% and 23%, respectively) and PET coated with unloaded pullulan (≈26% reduction in both coefficients). In spite of the presence of the filler, all of the coating formulations did not significantly impair the overall optical properties of the final material, which exhibited haze values below 3% and transmittance above 85%. The only exception to this was represented by the formulation with the highest loading of mica (1.5 wt %, which is ϕ ≈ 0.01). These findings revealed, for the first time, the potential of the NBB mica to produce nanocomposite coatings in combination with biopolymers for the generation of new functional features, such as transparent high oxygen barrier materials.

Deposition of organic molecules with vinylic group on hydrogenated Si(100)

Depositing a monolayer of molecules on top of the most important semiconductor material, i.e. silicon, in order to obtain hybrid heterostructures is the main purpose of this work. Aromatic and heteroaromatic molecules with a vinylic group reacting with hydrogenated silicon atoms on a Si(100) surface by a radical reaction promoted by heat are studied. The molecular grafting occurs through the vinylic function while preserving the original molecular structure and molecular properties. After depositing the organic materials samples are analysed with atomic force microscopy (AFM) in order to verify the coverage level, film thickness and topographic features.