Violeta Barranco

XPS study of the surface chemistry of conventional hot-dip galvanised pure Zn, galvanneal and Zn-Al alloy coatings on steel

This study uses X-ray photoelectron spectroscopy (XPS) to analyse the outer surfaces of galvanised, galfan and galvanneal metallic coatings obtained by hot dipping. Considerable aluminium segregation towards the surface, principally as Al2O3, has been seen in all the studied coatings. The aluminium content on the surface was surprisingly similar to or even greater than the zinc content, which is the major element in the chemical composition of these coatings. The formation of Al2O3 seems to prevent the oxidation of the zinc in the metallic coating.

Influence of the microstructure and topography on the barrier properties of oxide scales generated on blasted Ti6Al4V surfaces.

The long-term interfacial bond between an implant and bone may be improved by creating a rough surface on the implant in order to increase the surface area available for bone/implant apposition. A natural consequence of surface roughening is an increase in metal ion release, which is itself a surface dominated process. Based on this fact, the aim of this work is to study the influence of the microstructure and topography on the barrier properties of oxide scales thermally generated at 700 °C for 1h on Ti6Al4V surfaces after blasting with Al(2)O(3) particles (coarse) or SiO(2) and ZrO(2) particles (fine). The microstructural and topographical characterization of the thermally treated blasted surfaces has been studied by means of scanning electron microscopy coupled with energy dispersive X-ray analysis, contact profilometry and X-ray diffraction. The barrier properties and corrosion behaviour of the oxide layers have been studied by means of electrochemical impedance spectroscopy (EIS) in Hanks solution. Thermal treatment at 700 °C for 1h promotes the formation of oxide scales with different morphologies and crystalline structures depending on the degree of deformation of the blasted surface. The oxide scale grown on the finely blasted sample has a pine needle-like morphology which is mainly formed of anatase TiO(2). In contrast, the oxide scale grown on the coarsely blasted sample has a globular morphology formed mainly of rutile TiO(2). The differences in morphology, i.e. fine or coarse, of the oxide scales influence the corrosion response of the blasted thermally treated samples in Hanks solution. The EIS results permit evaluation of the different oxide scales from the capacitance and resistance values obtained in the high-frequency region and show a good correlation between the morphology and barrier properties. Oxidation treatment at 700 °C for 1h of Ti6Al4V samples coarsely blasted with Al(2)O(3) improves the corrosion behaviour due to an increase in the thickness of a compact, ordered and more structurally stable oxide scale. This is due to the globular morphology of the rutile (TiO(2)) structure maintaining an average surface roughness suitable for optimal osseo-integration with long-term interfacial bonding between the implant and bone.

In situ cell culture monitoring on a Ti–6Al–4V surface by electrochemical techniques

In this work, the in situ interaction between Ti-6Al-4V alloy and osteoblastic cells has been studied by electrochemical techniques as a function of time. The interaction has been monitored for cell adhesion and growth of human osteoblastic Saos-2 cells on Ti-6Al-4V samples. The study has been carried out by electrochemical techniques, e.g., studying the evolution of corrosion potential with exposure time and by electrochemical impedance spectroscopy. The impedance results have been analyzed by using different equivalent circuit models that simulate the interface state at each testing time. The adhesion of the osteoblastic cells on the Ti-6Al-4V alloy leads to surface areas with different cell coverage rates, thus showing the different responses in the impedance diagrams with time. The effect of the cells on the electrochemical response of Ti-6Al-4V alloy is clearly seen after 4 days of testing, in which two isolated and well-differentiated time constants are clearly observed. One of these is associated with the presence of the cells and the other with a passive film on the Ti-6Al-4V alloy. After 7 days of culture, the system is governed by a resistive component over a wide frequency range which is associated with an increase in the cell coverage rate on the surface due to the extracellular matrix.

Enhancing in vitro biocompatibility and corrosion protection of organic–inorganic hybrid sol–gel films with nanocrystalline hydroxyapatite

Application of novel organic-inorganic hybrid sol-gel coatings containing dispersed hydroxyapatite (HAp) particles improves the biocompatibility, normal human osteoblast (NHOst) response in terms of osteoblast viability and adhesion of a Ti6Al4V alloy routinely used in medical implants. The incorporation of HAp particles additionally results in more effective barrier proprieties and improved corrosion protection of the Ti6Al4V alloy through higher degree of cross-linking in the organopolysiloxane matrix and enhanced film thickness.

Biocompatibility and Corrosion Protection Behaviour of Hydroxyapatite Sol-Gel-Derived Coatings on Ti6Al4V Alloy

The aim of this work was to prepare hydroxyapatite coatings (HAp) by a sol-gel method on Ti6Al4V alloy and to study the bioactivity, biocompatibility and corrosion protection behaviour of these coatings in presence of simulated body fluids (SBFs). Thermogravimetric/Differential Thermal Analyses (TG/DTA) and X-ray Diffraction (XRD) have been applied to obtain information about the phase transformations, mass loss, identification of the phases developed, crystallite size and degree of crystallinity of the obtained HAp powders. Fourier Transformer Infrared Spectroscopy (FTIR) has been utilized for studying the functional groups of the prepared structures. The surface morphology of the resulting HAp coatings was studied by Scanning Electron Microscopy (SEM). The bioactivity was evaluated by soaking the HAp-coatings/Ti6Al4V system in Kokubo’s Simulated Body Fluid (SBF) applying Inductively Coupled Plasma (ICP) spectrometry. 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide (MTT) and Alamar blue cell viability assays were used to study the biocompatibility. Finally, the corrosion behaviour of HAp-coatings/Ti6Al4V system was researched by means of Electrochemical Impedance Spectroscopy (EIS). The obtained results showed that the prepared powders were nanocrystalline HAp with little deviations from that present in the human bone. All the prepared HAp coatings deposited on Ti6Al4V showed well-behaved biocompatibility, good bioactivity and corrosion protection properties.

Improvement of the adhesion between polyaniline and commercial carbon paper by acid treatment and its application in supercapacitor electrodes

Abstract Commercial carbon paper was coated with polyaniline (PANI) using in situ polymerization of aniline. Prior to the PANI coating, acid treatment was performed to carboxylate the surface of the carbon paper for enhancing PANI adhesion by sonication of the carbon paper in a mixture of concentrated sulfuric and nitric acids. The loading mass density of PANI on the acid-treated carbon paper increased more than three times compared to that on the carbon paper without acid treatment. The specific capacitance also increased from 112 to 174 F/g in a two-electrode system (calculated using a total mass of carbon paper and PANI) due to better PANI coating on the acid-treated carbon paper. The simple acid treatment provides good adhesion of PANI to the commercial carbon paper and can be applied to prepare supercapacitor electrodes.

Multifunctional sol-gel derived thin film based on nanocrystaline hydroxyapatite powders

The aim of this work was to prepare bioactive hydroxyapatite coatings by sol-gel method and to study the effect of thermal treatment temperature upon the bioactivity and corrosion protection of these coatings on Ti6Al4V alloy. The application of (DTA/TGA) and (XRD) has provided valuable information about the phase transformation, mass loss, identification of the phases developed, crystallite size and degree of crystallinity. (SEM/EDX) has been applied to study the surface morphology of coated samples before and after immersion in simulated body fluid (SBF) to detect the biomimetic precipitation of the bone- like apatite. The obtained results show that all the prepared samples are ceramic nanocrystalline with crystal structure and composition like hydroxyapatite, with little deviations from that present in the human bone. The bioactivity of the studied samples is found to be closely related to the thermal treatments applied. That is, the bioactivity decreases as the temperature of the thermal treatment increase. Coatings from such prepared hydroxyapatite sol have been accomplished by dip-coating technique on non-toxic Ti6Al4V alloy for biomedical applications. The corrosion behaviour of the resulting hydroxyapatite coatings in a (SBF) has been studied by electrochemical impedance spectroscopy (EIS). The hydroxyapatite coated Ti6Al4V alloy displayed excellent bioactivity when soaked in the (SBF) and acceptable corrosion protection behaviour.

Large-scale conversion of helical-ribbon carbon nanofibers to a variety of graphene-related materials

Helical-ribbon carbon nanofibers produced on an industrial scale were successfully converted in highly functionalized graphene nanoplatelets by using a slight modification of the Hummers oxidation method. The duration of the oxidative process severely affected the interlayer spacing in the resulting nanoplatelets and, consequently, they showed very different exfoliation behavior. Therefore, it was possible to obtain a variety of graphene-related products through their ultrasonication or thermal treatments such as exfoliation-reduction by flash-pyrolysis in air at temperatures between 400 and 1000 °C or standard activation with CO2 at 800 °C. Detailed comparison of the functionalized carbon nanoplatelets, graphene oxides, reduced graphene oxides and activated carbon nanoplatelets reveals the wide spectrum of their properties with specific surface areas in the range of 4–500 m2 g−1, oxygen content from 38 to 5 wt% and different structural ordering. This study also underlines the impact of the structural, textural and chemical changes experienced by the carbon nanofibers along the various processes on the performance as supercapacitor electrodes. This preliminary study, based on cyclic voltammetry in 2 M H2SO4 aqueous electrolyte, is a summary of the strengths and weaknesses of the different graphene-related materials for this application. The helical-ribbon carbon nanofibers displayed only 10 F g−1, the capacitance of the functionalized graphene nanoplatelets greatly rose to 104 F g−1 with clear contributions from pseudocapacitance. Values around 100–120 F g−1 were found for the graphene oxides and activated graphene nanoplatelets although a marked resistive character is detected. Flash-pyrolysis at 1000 °C leads to lower capacitance (79 F g−1) but much quicker charge propagation. Among all these materials, the lower-cost functionalized graphene nanoplatelets displayed the better behavior for aqueous supercapacitors.

Native Oxide Films on AZ31 and AZ61 Commercial Magnesium Alloys – Corrosion Behaviour, Effect on Isothermal Oxidation and Sol–gel Thin Film Formation

The authors present a review of their recent research work in an endeavour to interpret the influence of native oxide films on the corrosion behaviour of commercial AZ31 and AZ61 magnesium alloys or on the oxidation kinetics in air at 200°C. The tendency of some of these thin films to be sufficiently protective in mild or weak corrosive environments is examined. For obtaining oxide films with different protective properties, some of the specimens are tested with the surface in the as-received condition, while others are tested immediately after mechanical polishing. The technique applied to characterise thin (thickness of just a few nanometres) oxide films present on the surface of alloys has basically been XPS (X-ray photoelectron spectro‐ scopy) in combination with ion sputtering. Oxidation resistance of the alloys is quantified by thermo gravimetric (TG) curves and their corrosion rate is evaluated by Electrochemical Impedance Spectroscopy (EIS) and hydrogen evolution measure‐ ment in chloride solutions with different aggressivity. Emphasis is placed on the possible effects of: (a) the different thickness of the native oxide films formed on the polished surfaces on the corrosion behaviour of the alloys; and (b) the different film homogeneity and uniformity on the oxidation results. Finally, an attempt will be made to learn more about the influence of the native oxide films that cover the substrate on the subsequent growth and protective behaviour of the sol–gel coatings.

Triethylphosphite as a network forming agent enhances in vitro biocompatibility and corrosion protection of hybrid organic-inorganic sol-gel coatings for Ti6Al4V alloys

The biocompatibility and life of metallic implants can be enhanced through improving the biocompatibility and corrosion protection characteristics of the coatings used with these materials. In this study, triethylphosphite (TEP) was used to introduce phosphorus into organic-inorganic hybrid silica based sol-gel coatings prepared using γ-methacryloxypropyltrimethoxysilane and tetramethylorthosilicate. Addition of TEP dramatically increased the rate of intermolecular condensation and resulted in materials showing greater cross-linking. Protein (fibrinogen) uptake, osteoblast in vitro biocompatibility and corrosion resistance was enhanced in coatings containing TEP. Although higher concentrations of phosphorus supported the greatest improvement in biocompatibility, a compromise in the phosphorus concentration used would be required if corrosion resistance was most desirable parameter for optimisation. Films prepared by dip coating on Ti6Al4V alloys from these sols offer a promising alternative to wholly metallic prostheses.