Rosa Di Mundo

Nanotexturing of Polystyrene Surface in Fluorocarbon Plasmas: From Sticky to Slippery Superhydrophobicity

In this work plasma etching processes have been studied to roughen and fluorinate polystyrene surface as an easy method to achieve a superhydrophobic slippery character. Radiofrequency discharges have been fed with CF(4)/O(2) mixtures and the effect of the O(2):CF(4) ratio, the input power, and the treatment duration have been investigated in terms of wettability, with focus on sliding performances. For this purpose, surface morphological variations, evaluated by means of scanning electron microscopy and atomic force microscopy, together with the chemical assessment by X-ray photoelectron spectroscopy, have been correlated with water contact angle hysteresis and volume resolved sliding angle measurements. Results indicate that by increasing the height and decreasing the density of the structures formed by etching, within a tailored range, a transition from sticky to slippery superhydrophobicity occurs. A short treatment time (5 min) is sufficient to obtain such an effect, provided that a high power input is utilized. Optimized surfaces show a unaltered transparency to visible light according to the low roughness produced.

Melanin Layer on Silicon: an Attractive Structure for a Possible Exploitation in Bio-Polymer Based Metal- Insulator-Silicon Devices

Dr. M. Ambrico , Dr. P. F. Ambrico CNR-Istituto di Metodologie Inorganiche e dei Plasmi-UOS di Bari70125 Bari, Italy E-mail: marianna.ambrico@ba.imip.cnr.it Dr. A. Cardone , Dr. S. R. Cicco CNR-Istituto di Chimica dei Composti OrganoMetallici-UOS di Bari70125 Bari, Italy Ligonzo , Dr. . T Prof. Augelli . V Dipartimento Interateneo di FisicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy Dr. R. Di Mundo , Prof. G. M. arinola F Dipartimento di ChimicaUniversita degli Studi di Bari “Aldo Moro”70125 Bari, Italy

Cell Adhesion on Nanotextured Slippery Superhydrophobic Substrates

In this work, the response of Saos2 cells to polymeric surfaces with different roughness/density of nanometric dots produced by a tailored plasma-etching process has been studied. Topographical features have been evaluated by atomic force microscopy, while wetting behavior, in terms of water-surface adhesion energy, has been evaluated by measurements of drop sliding angle. Saos2 cytocompatibility has been investigated by scanning electron microscopy, fluorescent microscopy, and optical microscopy. The similarity in outer chemical composition has allowed isolation of the impact of the topographical features on cellular behavior. The results indicate that Saos2 cells respond differently to surfaces with different nanoscale topographical features, clearly showing a certain inhibition in cell adhesion when the nanoscale is particularly small. This effect appears to be attenuated in surfaces with relatively bigger nanofeatures, though these express a more pronounced slippery/dry wetting character.

Long-Lasting Antifog Plasma Modification of Transparent Plastics

Antifog surfaces are necessary for any application requiring optical efficiency of transparent materials. Surface modification methods aimed toward increasing solid surface energy, even when supposed to be permanent, in fact result in a nondurable effect due to the instability in air of highly hydrophilic surfaces. We propose the strategy of combining a hydrophilic chemistry with a nanotextured topography, to tailor a long-lasting antifog modification on commercial transparent plastics. In particular, we investigated a two-step process consisting of self-masked plasma etching followed by plasma deposition of a silicon-based film. We show that the deposition of the silicon-based coatings on the flat (pristine) substrates allows a continuous variation of wettability from hydrophobic to superhydrophilic, due to a continuous reduction of carbon-containing groups, as assessed by Fourier transform infrared and X-ray photoelectron spectroscopies. By depositing these different coatings on previously nanotextured substrates, the surface wettability behavior is changed consistently, as well as the condensation phenomenon in terms of microdroplets/liquid film appearance. This variation is correlated with advancing and receding water contact angle features of the surfaces. More importantly, in the case of the superhydrophilic coating, though its surface energy decreases with time, when a nanotextured surface underlies it, the wetting behavior is maintained durably superhydrophilic, thus durably antifog.

Influence of chemistry on wetting dynamics of nanotextured hydrophobic surfaces.

In this work, the role of a chemical parameter, such as the degree of fluorination, on the wetting behavior of nanotextured hydrophobic surfaces is investigated. Texture and chemistry tuning of the surfaces has been accomplished with single batch radiofrequency low-pressure plasma processes. Polystyrene substrates have been textured by CF(4) plasma etching and subsequently covered by thin films with a tunable F-to-C ratio, obtained in discharges fed with C(4)F(8)-C(2)H(4). Measurements of wetting dynamics reveal a regime transition from adhesive-hydrophobic to slippery-superhydrophobic, i.e., from wet to non wet states, as the F-to-C rises at constant topography. Such achievements are strengthened by calculation of the solid fraction of surface water contact area applying Cassie-Baxter advancing and receding equations to water contact angle data of textured and flat reference surfaces.

A water-soluble eumelanin polymer with typical polyelectrolyte behaviour by triethyleneglycol N-functionalization

N-functionalization of 5,6-dihydroxyindole with a hydrophilic triethyleneglycol (TEG) chain provides access to a new class of water-soluble eumelanin-like materials with relatively high dielectric constant and polyelectrolyte behaviour, reflecting enhanced charge transport by in-depth incorporation of hydration networks.

Plasma-Textured Teflon: Repulsion in Air of Water Droplets and Drag Reduction Underwater

A superhydrophobic behavior can be obtained by properly modifying the surface topography of Teflon or other fluorinated polymers having an inherent hydrophobic character. According to this strategy, we have micro/nanotextured Teflon both as plane material (sheets) and as three-dimensional (3D) object (spheres) with a single step plasma process. The obtained textured Teflon samples were compared with those made of pristine Teflon in air, in terms of repulsion of impacting water droplets, and underwater, in terms of air layer behavior under static and dynamic conditions. The latter case was investigated by subjecting the spheres to a vertical fall in water. Modified surfaces present nanofilaments on the top of micrometric vertical structures, which can increase the air retaining capacity, resulting in a biomimicry effect due to a similarity with the Salvinia molesta leaf. On this surface, repulsion of impacting water droplets can be as fast as previously reached only on heated solids. Also, the air layer over the modified spheres underwater is shown to play a role in the observed reduction of hydrodynamic drag onto the moving object.

Surface chemistry and morphology effects on optoelectronic transport at metal/nanostructured silicon/silicon structures

This work enlighten on the modification of the electrical and optoelectronic properties at metal/silicon interface, where the silicon surface is nanostructured by single step mask-less CF4 plasma in reactive ion etching mode. The electrical transport across metal/nanotextured silicon/silicon structure has been correlated with morphological variations of surface topological features and chemistry. The results evidence that such nanostructures enhance the photovoltaic behavior and affect electrical and optoelectronic transport to a different extent, depending not only on surface texturing but also on surface chemistry.

Electrical Transport Features of SiNWs Random Network on Si Support after Covalent Attachment of New Organic Functionalities

Modification of the electrical transport of a random network of silicon nanowires assembled on n-silicon support, after silicon nanowires functionalization by chlorination/alkylation procedure, is ...

Filamentary superhydrophobic Teflon surfaces: Moderate apparent contact angle but superior air-retaining properties.

HYPOTHESIS Micro-scale textured Teflon surfaces, resulting from plasma etching modification, show extremely high water contact angle values and fairly good resistance to water penetration when hit by water drops at medium-high speed. This behavior is more pronounced when these surfaces present denser and smaller micrometric reliefs. Tailoring the top of these reliefs with a structure which further stabilizes the air may further increase resistance to wetting (water penetration) under static and dynamic conditions. EXPERIMENTS Conditions of the oxygen fed plasma were tuned in order to explore the possibility of obtaining differently topped structures on the surface of the polymer. Scanning Electron Microscopy (SEM) was used to explore topography and X-ray Photoelectron Spectroscopy (XPS) to assess chemical similarity of the modified surfaces. Beside the usual advancing and receding water contact angle (WCA) measurements, surfaces were subjected to high speed impacting drops and immersion in water. FINDINGS At milder, i.e. shorter time and lower input power, plasma conditions formation of peculiar filaments is observed on the top of the sculpted reliefs. Filamentary topped surfaces result in a lower WCA than the spherical ones, appearing in this sense less superhydrophobic. However, these surfaces give rise to the formation of a more pronounced air layer when placed underwater. Further, when hit by water drops falling at medium/high speed, they show a higher resistance to water penetration and a sensitively lower surface-liquid contact time. The contact time is as low as previously observed only on heated solids. This behavior may be ascribed to the cavities formed beneath the filaments which, similarly with the salvinia leaf structures, require a surplus of pressure to be filled by water. Also, it suggests a different concept of superhydrophobicity, which cannot be expected on the basis of the conventional water contact angle characterization.