Na6Li4MO4(CO3)4 (M = W and Mo): An Alternative Electrolyte for High-Temperature Electrochemical Cells.

Two new acentric oxycarbonates Na6Li4MO4(CO3)4 (M = W and Mo) were synthesized via a conventional solid-state route. Their structure was determined from X-ray diffraction data on single crystals. Na6Li4MO4(CO3)4 (M = W and Mo) crystallizes in the acentric cubic P-43m space group (a ≈ 7.15 Å). It is composed of MLi4O16 units built from MO4 and LiO4 tetrahedra and linked by CO32- groups to form a three-dimensional framework in which Na+ ions are inserted. We showed from differential scanning calorimetry and powder X-ray diffraction experiments that the melting is congruent (T ∼525 °C). In the solid and molten forms, conductivity was measured for both oxycarbonates by electrochemical impedance spectroscopy with three various gas compositions (CO2 100 vol %, CO2-air 70-30 vol %, and CO2-air 20-80 vol %). Each time, the stability of the electrical behavior was checked via heating and cooling cycles. The conductivity of both solid and molten phases is purely ionic and in the same order of magnitude as for the classical molten alkali electrolyte made of Li-Na or Li-K carbonates. As activation energies are also comparable, those new oxycarbonates appear to be promising electrolytes for electrochemical devices.

Feasibility Synthesis and Characterization of Gadolinia Doped Ceria Coatings Obtained by Cathodic Arc Evaporation.

Gadolinia doped ceria coatings were elaborated by cathodic arc evaporation from a metallic Ce-Gd (90-10 at.%) target inserted into a conventional multiarc Ti evaporation target in the presence of a reactive argon-oxygen gas mixture. The structural and chemical features of these films were determined by x-ray diffraction and scanning electron microscopy. Their electrical properties were characterized using impedance spectroscopy measurements. It was shown that the as-deposited coatings crystallize in the fluorite type fcc structure of ceria and that their composition is the same as that of the target. The morphology of the coatings is influenced by the evaporation parameter (stress and droplet). The electrical measurements showed two contributions in Nyquist representation and the activation energy was slightly higher than that given in the literature data for the bulk material.

Functionalized Multi-Walled Carbon Nanotube-Based Aptasensors for Diclofenac Detection.

Driven by the increasing concern about the risk of diclofenac (DCF) residues as water pollutants in the aqueous environment and the growing need for its trace determination, a simple but sensitive electrochemical aptasensor for the trace detection of DCF was developed. To construct the aptasensor, the amine-terminated DCF aptamer was covalently immobilized on the surface of the carboxylic acid-functionalized multi-walled carbon nanotube (f-MWCNT)-modified glassy carbon electrode (GCE) through EDC/NHS chemistry. The f-MWCNTs provide a reliable matrix for aptamer immobilization with high grafting density, while the aptamer serves as a biorecognition probe for DCF. The obtained aptasensor was incubated with DCF solutions at different concentrations and was then investigated by electrochemical impedance spectroscopy (EIS). It displays two linear ranges of concentration for DCF detection, from 250 fM to 1pM and from 1 pM to 500 nM with an extremely low detection limit of 162 fM. Also, the developed biosensor shows great reproducibility, acceptable stability, and reliable selectivity. Therefore, it offers a simple but effective aptasensor construction strategy for trace detection of DCF and is anticipated to show great potential for environmental applications.

A Tribological and Ion Released Research of Ti-Materials for Medical Devices.

The increase in longevity worldwide has intensified the use of different types of prostheses for the human body, such as those used in dental work as well as in hip and knee replacements. Currently, Ti-6Al-4V is widely used as a joint implant due to its good mechanical properties and durability. However, studies have revealed that this alloy can release metal ions or particles harmful to human health. The mechanisms are not well understood yet and may involve wear and/or corrosion. Therefore, in this work, commercial pure titanium and a Ti-6Al-4V alloy were investigated before and after being exposed to a simulated biological fluid through tribological tests, surface analysis, and ionic dissolution characterization by ICP-AES. Before exposure, X-ray diffraction and optical microscopy revealed equiaxed α-Ti in both materials and ß-Ti in Ti-6Al-4V. Scratch tests exhibited a lower coefficient of friction for Ti-6Al-4V alloy than commercially pure titanium. After exposure, X-ray photoelectron spectroscopy and surface-enhanced Raman spectroscopy results showed an oxide film formed by TiO2, both in commercially pure titanium and in Ti-6Al-4V, and by TiO and Al2O3 associated with the presence of the alloys. Furthermore, inductively coupled plasma atomic emission spectroscopy revealed that aluminum was the main ion released for Ti-6Al-4V, giving negligible values for the other metal ions.

The effect of Staphylococcus aureus on the electrochemical behavior of porous Ti-6Al-4V alloy.

Ti-6Al-4V alloy has been widely investigated for biomedical applications due to its low density, high specific strength, and favorable corrosion resistance. However, some reported failures have imposed a challenge to improve bone regeneration and fixation, as well as antibacterial properties. A further opportunity for solving this problem is the introduction of porosity. However, this can induce metallic release and corrosion product formation. In this work, a Ti-6Al-4V alloy was exposed to Hank's solution, sterilized and inoculated with Staphylococcus aureus at 37 °C. Surface analysis was carried out by SEM-EDS and XPS. Electrochemical measurements were also performed using chronopotentiometry at open circuit potential, polarization curves, and electrochemical impedance spectroscopy. After exposure, FE-SEM showed some colonies of S. aureus on the sample with 22% porosity. However, XPS analysis revealed that the presence of bacterium influenced the composition of the oxide layer, even more drastically with the increase in added porosity. Moreover, the impedance analysis showed De Levie's behavior, revealing a reduction of pore resistance and modulus of the impedance in the low frequency range in inoculated medium, and polarization curves showed that the passivity potential range was decreased, whereas the passivity current increased in the presence of the S. aureus.

Effect of added porosity on a novel porous Ti-Nb-Ta-Fe-Mn alloy exposed to simulated body fluid.

Porous titanium materials have gained interest as prosthesis materials due to their similar mechanical properties to the human bone, biocompatibility, and high corrosion resistance. The presence of pores in the metal matrix implies a decrease in the elastic modulus and an increase in the active area, perhaps improving the osseointegration. Corrosion resistance is a critical consideration as corrosion may lead not only to mechanical failure but also the release of ions and/or particles to the bloodstream. In this work, a novel Ti-Nb-Ta-Fe-Mn alloy with varying percentage of porosity (25, 31 and 37 v/v%) was exposed to simulated body fluid (SBF) at 37 °C and its corrosion resistance was investigated using electrochemical techniques and surface analysis as a function of exposure time. Open circuit potential and polarization curves revealed that the effect of porosity was mainly on the shift of the corrosion potential to more negative values with a slight increase in the anodic current. A passive range was also observed, which was not influenced either by increased exposure time or increased porosity. Therefore, a change in the surface specific area could have taken place during the exposure, which is not necessarily related to a corrosion process. Moreover, a typical porous electrode behavior was identified by electrochemical Impedance spectroscopy, without any significant change over time. No release of metal ions was detected by on line ICP-AES, either at the open circuit potential or upon polarizing the samples up to 2 V vs. SCE, whereas only traces elements (Fe and Mn 1 nmol/s cm2) were detected in the electrolyte accumulating all released ions during 30 days of exposure. Additionally, the surface analysis showed thickening of the oxide layer with exposure time. Therefore, the stability of the passive layer and low release of ions indicate that the porous alloys are suitable for further study as prosthesis materials.

On the High Sensitivity of Corrosion Resistance of NiTi Stents with Respect to Inclusions: An Experimental Evidence.

In this study, the electrochemical breakdown potentials (E b) of NiTi stents were assessed in correlation to their nonmetallic inclusion fractions in the extra low inclusion (ELI) range (inclu.% < 1% in area fraction, average size <39 µm). Quantitative investigations were performed to study the role of nonmetallic inclusions during pitting corrosion. Two stent samples with different inclusion fractions were fabricated using commercial NiTi tubes for studying the corrosion and mechanism. A survey of seven commercial stents in Europe was also conducted. Dependence was observed between the breakdown potentials and the inclusion fractions in the ELI stent (inclu.% = 0.2-0.8%), in which the breakdown potentials were found to be inversely proportional to inclusion fractions and densities (E b dropped from ∼800 to ∼400 mV). No breakdown occurred on the samples using high-purity NiTi materials (inclu.% < 0.1%). The roles of inclusions in pitting mechanisms were investigated using scanning electron microscopy (SEM) characterizations. The microstructural evidence showed that the impact of TiC and Ti2NiO x was very different in the pitting process. A maximum inclu.% ≤ 0.9% was required for obtaining E b ≥ 600 mV to meet the Food and Drug Administrations (FDA's) in vivo safety acceptance (low risk up to 6 months postimplantation). The high-purity stents (inclu.% < 0.1%) did not exhibit corrosion susceptibility until 1000 mV, suggesting superior corrosion resistance and thus long-term in vivo safety.

A comprehensive DFT investigation of bulk and low-index surfaces of ZrO2 polymorphs.

The bulk structure, the relative stability, and the electronic properties of monoclinic, tetragonal, and cubic ZrO(2) have been studied from a theoretical point of view, through periodic ab initio calculations using different Gaussian basis sets together with Hartree-Fock (HF), pure Density Functional Theory (DFT), and mixed HF/DFT schemes as found in hybrid functionals. The role of a posteriori empirical correction for dispersion, according to the Grimme D2 scheme, has also been investigated. The obtained results show that, among the tested functionals, PBE0 not only provides the best structural description of the three polymorphs, but it also represents the best compromise to accurately describe both the geometric and electronic features of the oxide. The relative stability of the three phases can also be qualitatively reproduced, as long as thermal contributions to the energy are taken into account. Four low-index ZrO(2) surfaces [monoclinic (-111), tetragonal (101 and 111), and cubic (111)] have then been studied at this latter level of theory. Surface energies, atomic relaxations, and electronic properties of these surfaces have been computed. The most stable surface is the cubic one, which is associated to small relaxations confined to the outermost layers. It is followed by the monoclinic (-111) and the tetragonal (101), which have very similar surface energies and atomic displacements. The tetragonal (111) was instead found to be, by far, the less stable with large displacements not only for the outermost but also for deeper layers. Through the comparison of different methods and basis sets, this study allowed us to find a reliable and accurate computational protocol for the investigation of zirconia, both in its bulk and surfaces forms, in view of more complex technological applications, such as ZrO(2) doped with aliovalent oxides as found in solid oxide fuel cells.

Discussion on a percolating conducting network of a composite thin-film electrode (≤1 µm) for micro-solid oxide fuel cell application.

Ni/Gd0.1Ce0.9O(2-δ) (Ni/GDC) and La0.6Sr0.4Fe0.8Co0.2O(3-δ)/Gd0.1Ce0.9O(2-δ) (LSCF/GDC) porous thin-film electrodes with thicknesses between 120 and 500 nm were synthesized through templated sol-gel chemistry coupled with the dip-coating process and heat treatment. The thin films consist of two interpenetrated networks made of pores and inorganic materials. The porous structure was composed of multi-scale pores with dimensions ranging from macro- to nanosize and with an oriented columnar structure. The dimension of the percolation network is discussed as a function of the chemical nature of the percolating components and the particle/thickness ratio. A three-dimensional percolation network is achieved in the LSCF/GDC composite, while a two-dimensional percolation network is observed for the Ni/GDC composite. This difference is related to the microstructure of the composite thin film. An anisotropic columnar structure is observed for Ni/GDC, while an isotropic structure is achieved for LSCF/GDC.