A Critical Analysis on the Current Design Criteria for Cathodic Protection of Ships and Superyachts

Classification Society and ISO standard regulate the design of cathodic protection (CP) plans of ships and superyachts. However, due to shipyards’ long experience, the hull vessel protection plans often rely on an adaptation of previous CP designs for similar ships. This simple practice could expose ships to low protection or overprotection. Here, the protection plan of an existing 42 m superyacht is considered to highlight critical CP design issues. The numerical analysis gives evidence of discrepancies between the CP design proposed in accordance with ISO standard and the protection plan that was actually implemented. Indeed, for a proper protection plan, the anode weight according to the ISO standard is 2.7 kg, whereas the real protection plan uses a 7 kg anode. The numerical optimization highlights an optimal anode mass of 5 kg (−28.5% in weight). It provides sufficient protection for the expected lifetime, and will preserve the system in cases of damage to the hull and a consequent increase in the breakdown factor. This new solution underlines the importance and necessity of improving cathodic protection plan design

Cu(II) and Zn(II) complexes with hyaluronic acid and its sulphated derivative.Effect on the motility of vascular endothelial cells.

With the aim of improving the compatibility of biomaterials to be used for the construction of cardiovascular prosthesis, we have designed bioactive macromolecules resulting from chemical modifications of hyaluronic acid (Hyal). The stability constants of Cu(II) and Zn(II) complexes with the sulphated derivative of hyaluronic acid (HyalS3.5) were evaluated. Two different complexes have been found for each metal ion, CuL, Cu(OH)2L and ZnL, Zn(OH)2L (L means the disaccharide unit of the ligands) in aqueous solution at 37 degrees C. The dihydroxo Cu(II) complex was present in high percentage at pH=7.4. On the contrary, the Zn(II) ion was present with a relatively low percentage of both complexes. The ability to stimulate endothelial cell adhesion and migration was evaluated for Hyal, HyalS3.5 and their complexes with Cu(II) and Zn(II) ions. The results revealed that Hyal and [Cu(OH)2HyalS3.5](4.5)- induced cell adhesion, while [ZnHyalS3.5](2.5)- and [Zn(OH)2HyalS3.5](4.5)- inhibited the process. The chemotactic activity of increasing concentrations of the above complexes was also evaluated, demonstrating that [Cu(OH)2HyalS3.5](4.5)- complex at 1 microM concentration was the most active in inducing cell migration. These results have been also strengthened by analysing adherent cell migration in agarose. In conclusion, sulphated hyaluronic acid coordinated to Cu(II) seems to be a promising matrix molecule for the construction of cardiovascular prosthesis.

Experimental approach for the study of SOFC cathodes

The suitability of impedance measurements in Solid Oxide Fuel Cells (SOFCs) is an important concern, especially in case of measuring separately the behaviour of one of the electrode when an overvoltage is applied. In this case a thin electrolyte-supported cell with the RE (Reference Electrode) coplanar with the WE (Working Electrode) is experimentally convenient, but many authors highlighted that incorrect results can be obtained if an inappropriate geometric configuration is used. In this work LSM cathodes ((La0.8Sr0.2)MnO3-x) were investigated in a Yttria-stabilised Zirconia (YSZ) electrolyte-supported cell, using an electrolyte 3 mm thick. Two types of cells were prepared: the first (Cell1) according to the geometric requirements suggested in literature: little WE (diameter 3 mm) aligned to the CE (Counter Electrode) and with equal Rpol(polarisation resistance) and time constant; RE co-planar around the WE and placed at a distance greater than three-electrolyte thicknesses from the WE; the second one (Cell2) equal to Cell1 but with a bigger WE (diameter 8 mm). Impedance measurements were carried out both in two- and three- electrode configuration, at OCV (Open Circuit Voltage) and under applied overpotentials. A preliminary comparison between the results extracted from Cell2 at two- and three- electrodes confirms that a thick electrolyte allows extracting suitable three-electrode impedance results in case of OCV and small overpotentials. On the other side, when an overpotential over 0.2 V is applied, a comparison between Cell1 and Cell2 gives quite different results. The investigation here presented considers also an experimental approach useful for the comprehension of the main phenomena governing the kinetic of the process

Characterisation of La0.6Sr0.4Co0.2Fe0.8O3-\u3b4- Ba0.5Sr0.5Co0.8Fe0.2O3-\u3b4composite as cathode for solid oxide fuel cells

Mixture of La0.6Sr0.4Co0.2Fe0.8O3-\u3b4 and Ba0.5Sr0.5Co0.8Fe0.2O3-\u3b4, was investigated as promising cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The two perovskites possess high catalytic activity for the oxygen reduction (ORR), although some problems related to their chemical and structural stability have still to be overcome in view of improving durability of the cell performance. The achievement of a stable and high-performing composite material is the aim of this study. In principle, chemical equilibrium at the LSCF-BSCF interface may be reached through ions interdiffusion during the sintering process, resulting in the chemical stabilization of the material. The composite-cathode deposited on Ce0.8Sm0.2O2-\u3b4 electrolyte was then investigated by Electrochemical Impedance Spectroscopy (EIS) as a function of temperature, overpotential and time. The results exhibited an interesting electrochemical behavior of the electrode toward oxygen reduction reaction. XRD analysis was performed to detect structural modification during thermal or operation stages and it was found that after the sintering the two starting perovskites were no longer present; a new phase with a rhombohedral La0,4Sr0,6FeO3-type structure (LSF) is formed. An improvement in composite cathode durability has been detected under the considered operating conditions (200 mAcm-2, 700 \ub0C) in comparison with the pure BSCF electrode. The results confirmed this new electrode as promising system for further investigation as IT-SOFC cathode

Application of electro-fenton process for the treatment of methylene blue

The electrochemical removal of an aqueous solution containing 0.25 mM of methylene blue (MB), one of the most important thiazine dye, has been investigated by electro-Fenton process using a graphite-felt cathode to electrogenerate in situ hydrogen peroxide and regenerate ferrous ions as catalyst. The effect of operating conditions such as applied current, catalyst concentration, and initial dye content on MB degradation has been studied. MB removal and mineralization were monitored during the electrolysis by UV\u2013Vis analysis and TOC measurements. The experimental results showed that MB was completely removed by the reaction with \u2022OH radicals generated from electrochemically assisted Fenton\u2019s reaction, and in any conditions the decay kinetic always follows a pseudo-first-order reaction. The faster MB oxidation rate was obtained applying a current of 300 mA, with 0.3 mM Fe2+at T=35 \ub0C. In these conditions, 0.25 mM MB was completely removed in 45 min and the initial TOC was removed in 90 min of electrolysis, meaning the almost complete mineralization of the organic content of the treated solution

A Comprehensive Approach to Improve Performance and Stability of State-of-the- Art Air Electrodes for Intermediate Temperature Reversible Cells: An Impedance Spectroscopy Analysis

Solid oxide fuel cells (SOFC) are devices for the transformation of chemical energy in electrical energy. SOFC appear very promising for their very high efficiency, in addition to the capability to work in reverse mode, which makes them suitable for integration in production units powered with renewables. Research efforts are currently addressed to find chemically and structurally stable materials, in order to improve performance stability during long-term operation. In this work, we examine different approaches for improving stability of two state-of-the-art perovskite materials, La0.6Sr0.4Co0.2Fe0.8O3-\uf064 (LSCF) and Ba0.5Sr0.5Co0.8Fe0.2O3-\uf064 (BSCF), very promising as air electrodes. Two different systems are considered: (i) LSCF and BSCF porous electrodes impregnated by a nano-sized La0.8Sr0.2MnO3-\uf064 layer and (ii) LSCF-BSCF composites with the two phases in different volume proportions. The study considers the results obtained by electrochemical impedance spectroscopy investigation, observing the polarisation resistance (Rp) of each system to evaluate performance in typical SOFC operating conditions. Furthermore, the behaviour of polarisation resistance under the effect of a net current load (cathodic) circulating for hundreds of hours is examined, as parameter to evaluate long-term performance stability

Spatially controlled cell adhesion on three-dimensional substrates

The microenvironment of cells in vivo is defined by spatiotemporal patterns of chemical and biophysical cues. Therefore, one important goal of tissue engineering is the generation of scaffolds with defined biofunctionalization in order to control processes like cell adhesion and differentiation. Mimicking extrinsic factors like integrin ligands presented by the extracellular matrix is one of the key elements to study cellular adhesion on biocompatible scaffolds. By using special thermoformable polymer films with anchored biomolecules micro structured scaffolds, e.g. curved and µ-patterned substrates, can be fabricated. Here, we present a novel strategy for the fabrication of µ-patterned scaffolds based on the “Substrate Modification and Replication by Thermoforming” (SMART) technology: The surface of a poly lactic acid membrane, having a low forming temperature of 60°C and being initially very cell attractive, was coated with a photopatterned layer of poly(L-lysine) (PLL) and hyaluronic acid (VAHyal) to gain spatial control over cell adhesion. Subsequently, this modified polymer membrane was thermoformed to create an array of spherical microcavities with diameters of 300 µm for 3D cell culture. Human hepatoma cells (HepG2) and mouse fibroblasts (L929) were used to demonstrate guided cell adhesion. HepG2 cells adhered and aggregated exclusively within these cavities without attaching to the passivated surfaces between the cavities. Also L929 cells adhering very strongly on the pristine substrate polymer were effectively patterned by the cell repellent properties of the hyaluronic acid based hydrogel. This is the first time cell adhesion was controlled by patterned functionalization of a polymeric substrate with UV curable PLL-VAHyal in thermoformed 3D microstructures

The Relative Importance of Topography and RGD Ligand Density for Endothelial Cell Adhesion

The morphology and function of endothelial cells depends on the physical and chemical characteristics of the extracellular environment. Here, we designed silicon surfaces on which topographical features and surface densities of the integrin binding peptide arginine-glycine-aspartic acid (RGD) could be independently controlled. We used these surfaces to investigate the relative importance of the surface chemistry of ligand presentation versus surface topography in endothelial cell adhesion. We compared cell adhesion, spreading and migration on surfaces with nano- to micro-scaled pyramids and average densities of 6×102–6×1011 RGD/mm2. We found that fewer cells adhered onto rough than flat surfaces and that the optimal average RGD density for cell adhesion was 6×105 RGD/mm2 on flat surfaces and substrata with nano-scaled roughness. Only on surfaces with micro-scaled pyramids did the topography hinder cell migration and a lower average RGD density was optimal for adhesion. In contrast, cell spreading was greatest on surfaces with 6×108 RGD/mm2 irrespectively of presence of feature and their size. In summary, our data suggest that the size of pyramids predominately control the number of endothelial cells that adhere to the substratum but the average RGD density governs the degree of cell spreading and length of focal adhesion within adherent cells. The data points towards a two-step model of cell adhesion: the initial contact of cells with a substratum may be guided by the topography while the engagement of cell surface receptors is predominately controlled by the surface chemistry