In situ corrosion monitoring of Ti–6Al–4V alloy in H2SO4/HCl mixed solution using electrochemical AFM

Electrochemical atomic force microscope (ECAFM) was employed for in situ observation of corrosion of solution annealed and furnace cooled Ti–6Al–4V titanium alloy in 0.5 mol l⁻¹ H₂SO₄ + 1 mol l⁻¹ HCl mixed solution. A scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) was also used for microstructure examination and chemical composition analysis. For solution annealed followed by furnace-cooled Ti–6Al–4V titanium alloy, selective corrosion of α phase and galvanic effect at α/β interface could be clearly observed at open circuit potential under ECAFM. A higher dissolution rate was also found in α phase than β phase on the bare Ti–6Al–4V titanium alloy. The effect of potential on the corrosion behavior was also explored. Negligible corrosion was found after potentiostatic etching at −0.5 and −0.85 V_Pt for 120 min. However, selective dissolution of α phase with respect to β phase occurred when the potential was controlled at −0.9 V_Pt. The polarity inversion during potentiostatic etching at −0.9 V_Pt was also found and discussed in this study.     

Corrosion resistance of anodic oxides on the Ti-50Zr and Ti-13Nb-13Zr alloys

Electrochemical analyses on the biocompatible alloys Ti-50Zr and Ti-13Nb-13Zr, as-cast and heat-treated, in distinct electrolytes (simulating or not physiological media: pH 7, Ringer, PBS, phosphate buffer and Na₂SO₄ solutions; pH 1, H₂SO₄, HNO₃, CH₃SO₃H, HClO₄ and H₃PO₄ solutions) are reported. Analyses of the open-circuit potential values indicated that either as-cast or heat-treated samples of both alloys present the same tendency to spontaneously form an oxide film on their surfaces and that the oxide grown in the Na₂SO₄ solution presents better protection characteristics than those formed in the phosphate buffer, Ringer and PBS solutions, in this order. Cyclic voltammograms obtained in the Ringer and PBS solutions showed that the Ti-13Nb-13Zr alloy does not transpassivate up to potentials of 8 V (versus SCE), while the Ti-50Zr alloy presents corrosion at potentials lower than 2 V (versus SCE), indicating that this alloy is less resistant to corrosion in solutions simulating physiological conditions. The obtained pit potential values showed that the heat treatment has very little influence on the corrosion behavior of the alloys. Finally, both alloys did not present transpassivation at potentials up to 8 V (versus SCE) in the H₂SO₄, HNO₃, CH₃SO₃H and H₃PO₄ solutions; however, when immersed in the HClO₄ solution the Ti-50Zr alloy underwent pit corrosion while the Ti-13Nb-13Zr alloy remained corrosion resistant in this potential range.     

Nb–TiO2 supported platinum nanocatalyst for oxygen reduction reaction in alkaline solutions

Platinum based nanocatalyst at home made Nb–TiO₂ support was synthesized and characterized as the catalyst for oxygen reduction reaction in 0.1 mol dm⁻³ NaOH, at 25 °C. Nb doped TiO₂ catalyst support, containing 5% of Nb, has been synthesized by modified acid-catalyzed sol–gel procedure in non-aqueous medium. BET and X-ray diffraction (XRD) techniques were applied for characterization of synthesized supporting material. XRD analysis revealed only presence of anatase TiO₂ phase in synthesized support powder. Existence of any peaks belonging to Nb compounds has not been observed, indicating Nb incorporated into the lattice.Nb–TiO₂ supported Pt nanocatalyst synthesized, using borohydride reduction method, was characterized by TEM and HRTEM techniques. Platinum nanoparticles distribution, over Nb doped TiO₂ support, was quite homogenous. Mean particle size of about 4 nm was found with no pronounced particle agglomeration. Electrochemical techniques: cyclic voltammetry and linear sweep voltammetry at rotating disc electrode were applied in order to study kinetics and estimate catalytic activity of this new catalyst for the oxygen reduction reaction in alkaline solution. Two different Tafel slopes were found: one close to −90 mV dec⁻¹ in low current density region and other approximately −200 mV dec⁻¹ in high current density region, which is in good accordance with literature results for oxygen reduction at Pt single crystals, as well as Pt nanocatalysts in alkaline solutions. Similar specific catalytic activity (expressed in term of kinetic current density per real surface area) of Nb(5%)–TiO₂/Pt catalyst for oxygen reduction reaction in comparison with the carbon supported platinum (Vulcan/Pt) nanocatalyst, was found.     

In vitro corrosion and mineralization of novel Ti–Si–C alloy

The in vitro electrochemical behaviour of a new titanium based α-alloy (Ti–0.5 wt% Si–0.65 wt% C), fabricated via casting and rapid cooling route, was determined using linear, Tafel, potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS), complemented with ex situ SEM-EDS analysis to evaluate the corrosion mechanism. The experimental results revealed that silicon and carbon, in addition to titanium, resulted in the enhancement of mechanical properties. The polarization tests confirmed that Ti–Si–C alloy possessed excellent corrosion resistance (a low corrosion current density of 0.033 μA cm⁻²), comparable to cp Ti and better than Ti6Al4V in phosphate buffered saline (PBS). The mechanism of corrosion was identified as selective dissolution of titanium solid solution matrix. EIS studies indicated the formation of a stable, passive oxide film on the alloy. Further, in vitro bioactivity was evaluated using mineralization tests i.e. by immersing the pre-treated alloy in a concentrated simulated body fluid (10× SBF). Chemical and microstructural characterization of the mineral layer, formed during immersion, revealed the deposition of fine, porous micron-sized globules of a phase rich in calcium-phosphate (Ca-P). In summary, the bulk properties and excellent in vitro electrochemical and mineralization behaviour of the as-cast Ti–Si–C alloy reveal a high potential for its application as load bearing metallic implants.     

Modification of titanium oxide layer by calcium and phosphorus

The aim of the study was to investigate the possibility of calcium and phosphorus ion implantation into an oxide film applied onto titanium during anodic passivation. The corrosion resistance of modified titanium in Tyrode's physiological solution has been identified. Anodic oxidation was carried out in two solutions. The first contained 20 g dm⁻³ NaH₂PO₂ in 4.3 M H₃PO₄ (K1), whereas the other, 20 g dm⁻³ Ca(H₂PO₂)₂ in 4.3 M H₃PO₄ (K2). Voltage of 100 and 150 V was applied. It has been found out that it is possible to incorporate Ca and P into the emerging passive layer. The application of the voltage of 150 V makes it very porous. It has been also demonstrated that titanium so modified presents higher resistance to corrosion in the investigated environment than titanium not modified in Tyrode's solution.     

Environmentally safe corrosion inhibition of Mg–Al–Zn alloy in chloride free neutral solutions by amino acids

The corrosion inhibition of Mg–Al–Zn alloy was investigated in stagnant naturally aerated chloride free neutral solutions using amino acids as environmentally safe corrosion inhibitors. The corrosion rate was calculated in the absence and presence of the corrosion inhibitor using the polarization technique and electrochemical impedance spectroscopy. The experimental impedance data were fitted to theoretical data according to a proposed electronic circuit model to explain the behavior of the alloy/electrolyte interface under different conditions. The corrosion inhibition process was found to depend on the adsorption of the amino acid molecules on the metal surface. Phenyl alanine has shown remarkably high corrosion inhibition efficiency up to 93% at a concentration of 2 × 10⁻³ mol dm⁻³. The corrosion inhibition efficiency was found to depend on the concentration of the amino acid and its structure. The mechanism of the corrosion inhibition process was discussed and different adsorption isotherms were investigated. The free energy of the adsorption process was calculated for the adsorption of different amino acids on the Mg–Al–Zn alloy and the obtained values reveal a physical adsorption of the inhibitor molecules on the alloy surface.     

Transparent Al–In–Zn–O Oxide semiconducting films with various in composition for thin-film transistor applications

Al–In–Zn–O thin-film transistors were fabricated. To examine the effect of In composition, we adopted a co-sputtering method using Al–Zn–O and In₂O₃ targets. The sputtering power of In₂O₃ was varied to 200, 150, and 50 W. The mobility and turn-on voltage of each device were 27.8 cm²V⁻¹ s⁻¹ and −4.2 V, 4.5 cm²V⁻¹ s⁻¹ and −3.5 V, 0.7 cm²V⁻¹ s⁻¹ and −3 V, respectively. We also investigated instabilities under negative gate bias stress (NBS) and negative bias illumination stress (NBIS). While the NBS was not influenced by the In contents, the NBIS characteristics were optimized for the device with In₂O₃ sputtering at 150 W.     

A highly sensitive ascorbic acid sensor using a Ni–Pt electrode

An amperometric sensor that measured ascorbic acid by the oxidation of the ascorbic acid on a Ni–Pt electrode was fabricated. The Ni component of the Ni–Pt alloy played a crucial role as a modifier that developed an erinaceous surface, which enlarged the sensing area and increased the sensitivity of the electrode. The Pt₈₂Ni₁₈ electrode exhibited the best sensitivity of 333 μA cm⁻² mM⁻¹ for ascorbic acid sensing. This electrode was further tested for reproducibility of the sensitivity, endurance, and interference; it exhibited excellent performance compared with electrodes reported in the literature.     

Chitosan–Fe3O4 nanocomposite based electrochemical sensors for the determination of bisphenol A

This paper reports the application of chitosan–Fe₃O₄ (CS–Fe₃O₄) nanocomposite modified glassy carbon electrodes for the amperometric determination of bisphenol A (BPA). We observed that the CS–Fe₃O₄ nanocomposite could remarkably enhance the current response and decrease its oxidation overpotential in the electrochemical detection. Experimental parameters, such as the amount of the CS–Fe₃O₄, the accumulation potential and time, the pH value of buffer solution etc. were optimized. Under the optimized conditions, the oxidation peak current was proportional to BPA concentration in the range between 5.0 × 10⁻⁸ and 3.0 × 10⁻⁵ mol dm⁻³ with the correlation coefficient of 0.9992 and the limit of detection of 8.0 × 10⁻⁹ mol dm⁻³ (S/N = 3). The proposed sensors were successfully employed to determine BPA in real plastic products and the recoveries were between 92.0% and 06.2%. This strategy might open more opportunities for the electrochemical determination of BPA in practical applications. Additionally, the leaching studies of BPA on incubation time using the as-prepared modified electrode were successfully carried out.     

Morphologies of nanostructured TiO2 doped with F on Ti–6Al–4V alloy

The formation of nanotubes in sulphuric/hydrofluoric acid electrolyte at controlled voltage is investigated on Ti–6Al–4V alloy used for load-bearing prosthetic applications. The effects of anodizing time and voltage on film morphology, composition and microstructure are studied by scanning and transmission electron microscopy, Rutherford backscattering spectroscopy (RBS), and Raman spectroscopy. Fluorine content in the films was of a particular interest for enhancement of antibacterial properties of the surface. The efficiencies of film formation are determined as about 40% and 80% for anodizing at 20 V and 60 V respectively for shorter anodizing time and as about 1 and 5% for longer anodizing time. For 5 min of anodizing, higher voltage conditions results in a thicker barrier layer. At extended anodizing time a further disruption of the nanotubular morphology and formation of approximately 1.5 μm-thick nanoporous film is promoted. The films grown at 20 V contain from 4 at.% to 6 at.% of fluorine. RBS detects about 13 at.% of fluorine incorporated in the film formed at 60 V for 60 min, possibly associated with a greater film thickness. The oxide film material consists of amorphous titania matrix doped with V₂O₅ and Al₂O₃.     

Preparation and Electrocatalytic Application of Composites Containing Gold Nanoparticles Protected with Rhodium-Substituted Polyoxometalates

Substitution of a metal center of phosphomolybdate, PMo₁₂O₄₀³⁻ (PMo₁₂), or its tungsten analogue with dirhodium(II) and subsequent stabilization of gold nanoparticles, AuNPs, with Rh₂PMo₁₁ are demonstrated. The AuNP-Rh₂PMo₁₁ mediates oxidations but adsorbs too weakly for direct modification of electrode materials. Stability in quiescent solution was achieved by modifying glassy carbon (GC) with 3-aminopropyltriethoxysilane (APTES) and then electrostatically assembling AuNP-Rh₂PMo₁₁. At GC|APTES|AuNP-Rh₂PMo₁₁, cyclic voltammetry showed the expected set of three reversible peak-pairs for PMo₁₁ in the range −0.2 to 0.6 vs. (Ag/AgCl)/V and the reversible Rh^II,III couple at 1.0 vs. (Ag/AgCl)/V. The presence of AuNPs increased the current for the reduction of bromate by a factor of 2.5 relative to that at GC|Rh₂PMo₁₁, and the electrocatalytic oxidation of methionine displayed characteristics of synergism between the AuNP and Rh^II. To stabilize AuNP-Rh₂PMo₁₁ on a surface in a flow system, GC was modified by electrochemically assisted deposition of a sol–gel with templated 10-nm pores prior to immobilizing the catalyst in the pores. The resulting electrode permitted determination of bromate by flow-injection amperometry with a detection limit of 4.0 × 10⁻⁸ mol dm⁻³.     

Electro-oxidation of ethylene glycol on nanoporous Ti–Cu amorphous alloy

This work describes ethylene glycol (EG) electro-oxidation over nanoporous structure catalyst prepared by dealloying Ti–Cu amorphous alloy. Scanning electron microscopy (SEM) was used to characterize nanoporous catalysts. Electrocatalytic performances in acid and alkaline mediums were measured by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The results showed that nanoporous Ti–Cu amorphous alloy exhibited apparent electrocatalytic ability in terms of higher oxidation current in CV and CA curves comparing to raw Ti–Cu amorphous alloy. Electro-oxidation of EG took place more easily in alkaline medium than that in acid medium. In acid medium, heat treatment improved the electrocatalytic activity of nanoporous catalyst. In alkaline medium, heat treatment played an enhancing role below 0.1 V and a depressing role above 0.1 V. Possible electro-oxidation mechanism of EG was also discussed.     

Anodic dissolution of U, Zr and U–Zr alloy and convolution voltammetry of Zr|Zr couple in molten LiCl–KCl eutectic

The anodic dissolution of U and Zr metal was studied in LiCl–KCl–UCl₃ and LiCl–KCl–ZrCl₄, respectively, at 773 K by cyclic voltammetry and compared with their respective dissolution behaviour in blank LiCl–KCl eutectic. The anodic dissolution of U–Zr alloy in LiCl–KCl–UCl₃ was also studied at 773 K to compare with the dissolution of U and Zr. The transfer coefficients evaluated by Tafel analysis and the method of Allen–Hickling for U and Zr dissolution were found to be in fair agreement with each other. U dissolution in LiCl–KCl–UCl₃ and Zr dissolution LiCl–KCl–ZrCl₄ were also studied by chronoamperometry and the diffusion coefficient value of U³⁺ was calculated to be in the range of 2.9 × 10⁻⁵ to 3.3 × 10⁻⁵ cm² s⁻¹ which is in agreement with those reported in literature. Convolution voltammetric analysis of Zr⁴⁺/Zr²⁺ redox couple in LiCl–KCl–ZrCl₄ was carried out for the first time to have a comprehensive understanding of the electrode kinetics.     

Effect of surface modification using various acids on electrodeposition of lithium

Sulface modification of lithium was carried out using the chemical reaction of the native film with acids (HF, H₃PO₄, HI, HCl) dissolved in propylene carbonate (PC). The chemical composition change of the lithium surface was detected using X-ray photoelectron spectroscopy. The electrodeposition of lithium on the as-received lithium or the modified lithium was conducted in PC containing 1.0 mol dm^–3 LiClO₄ or LiPF₆ under galvanostatic conditions. The morphology of electrodeposited lithium particles was observed with scanning electron microscopy. The lithium dendrites were observed when lithium was deposited on the as-received lithium in both electrolytes. Moreover the dendrites were also formed on the lithium surface modified with H₃PO₄, HI, or HCl. On the other hand, spherical lithium particles were produced, when lithium was electrodeposited in PC containing 1.0 mol dm^–3 LiPF₆ on the lithium surface modified with HE However spherical lithium particles were not obtained, when PC containing 1.0 mol dm^–3 LiClO₄ was used as the electrolyte. The lithium surface modified by H₃PO₄, HI, or HCl was covered with a thick film consisting of Li₃PO₄, Li₂CO₃, LiOH, or Li₂O. The lithium surface modified with HF was covered with a thin bilayer structure film consisting of LiF and Li₂O. These results clearly show that the surface film having the thin bilayer structure (LiF and Li₂O) and the use of PC containing 1.0 mol dm^–3 LiPF₆ enhance the suppression of dendrite formation of lithium.     

Studies on plasma sprayed bi-layered ceramic coating on bio-medical Ti-13Nb-13Zr alloy

Biomedical Ti alloys are prone to undergo degradation due to the combined effect of wear and corrosion. To overcome these problems, surface modification techniques are being used. In this paper, the biomedical Ti alloy Ti-13Nb-13Zr was plasma sprayed with nanostructured Al₂O₃-13 wt%TiO₂, yttria stabilized zirconia powders and bilayer containing alternate layers of the two coatings to improve the corrosion resistance and microhardness of the substrate. The plasma sprayed coatings were characterized by X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The microstructure, microhardness and surface roughness of the coatings were investigated. The corrosion resistance of the coatings was studied in simulated body conditions. The results show improved corrosion resistance for the bilayered coating compared to the individual plasma sprayed coatings on biomedical Ti-13Nb-13Zr alloy substrate.     

Electrochemical performance of Li3V2(PO4)3/C cathode materials using stearic acid as a carbon source

The Li₃V₂(PO₄)₃/C cathode materials are synthesized by a simple solid-state reaction process using stearic acid as both reduction agent and carbon source. Scanning electron microscopy and transmission electron microscopy observations show that the Li₃V₂(PO₄)₃/C composite synthesized at 700 °C has uniform particle size distribution and fine carbon coating. The Li₃V₂(PO₄)₃/C shows a high initial discharge capacity of 130.6 and 124.4 mAh g⁻¹ between 3.0 and 4.3 V, and 185.9 and 140.9 mAh g⁻¹ between 3.0 and 4.8 V at 0.1 and 5 C, respectively. Even at a charge–discharge rate of 15 C, the Li₃V₂(PO₄)₃/C still can deliver a discharge capacity of 103.3 and 112.1 mAh g⁻¹ in the potential region of 3.0–4.3 V and 3.0–4.8 V, respectively. Based on the analysis of cyclic voltammograms and electrochemical impedance spectra, the apparent diffusion coefficients of Li ions in the composites are in the region of 1.09 × 10⁻⁹ and 4.95 × 10⁻⁸ cm² s⁻¹.     

Effects of synthetic route on structure and electrochemical performance of Li3V2(PO4)3/C cathode materials

Three different synthetic routes, including solid-state reaction, sol–gel and hydrothermal methods are successfully used for preparation of Li₃V₂(PO₄)₃/C. Ascorbic acid is used as a reducing agent and/or as a chelating agent. The Li₃V₂(PO₄)₃/C synthesized by hydrothermal method with fine particles exhibits lower impedance and smaller potential difference values between oxidation and reduction peaks than those by solid-state reaction and sol–gel methods. Thus as cathode material for Li-ion batteries, the Li₃V₂(PO₄)₃/C synthesized by hydrothermal method shows higher discharge capacity, better rate capability and cyclic performance. Even at a high charge–discharge rate of 10 C, it still can deliver a discharge capacity of 101.4 mAh g⁻¹ and 106.6 mAh g⁻¹ in the potential range of 3.0–4.3 V and 3.0–4.8 V, respectively. The hydrothermal synthesis has been considered to be a competitive process to prepare Li₃V₂(PO₄)₃/C cathode materials with excellent electrochemical performances.     

Tris (2,2′-bipyridil) copper (II) chloride complex: a biomimetic tyrosinase catalyst in the amperometric sensor construction

The use of tris (2,2′-bipyridil) copper (II) chloride complex, [Cu(bipy)₃]Cl₂·6H₂O, as a biomimetic catalyst, is reported in the construction of an amperometric sensor for dopamine. The sensor was prepared modifying a glassy carbon electrode with a Nafion® membrane doped with the complex. The optimized conditions for the sensor response were obtained in 0.25 mol dm⁻³ Pipes buffer (pH 7.0) containing 150 μmol dm⁻³ H₂O₂, with an applied potential of −50 mV versus saturated calomel electrode (SCE). In these conditions, a linear response range between 9 and 230 μmol dm⁻³, with a sensitivity of 1.43±0.01 nA dm³ μmol⁻¹ cm⁻² and a detection limit of 4.8 μmol dm⁻³ were observed for dopamine. The response time for this sensor was about 1 s, presenting the same response for at least 150 successive measurements, with a good repeatability (4.8%) expressed as relative standard deviation for n=13. After its construction, this sensor can be used after 180 days without loss of sensitivity, kept at room temperature. The difference of the sensor response between four preparations was 4.2%. A detailed investigation about the sensor response for other eighteen phenolic compounds and five interfering species was performed. The sensor was applied for dopamine determination in pharmaceutical preparation with success.     

Anodic film growth on tantalum in dilute phosphoric acid solution at 20 and 85 °C

The effects of current density and temperature on the anodic films formed on tantalum in dilute H₃PO₄ (0.06%wt) solution have been studied by transmission electron microscopy, using ultramicrotomed sections, and Rutherford backscattering spectroscopy. Two-layered films have been identified, comprising an inner relatively pure Ta₂O₅ layer, adjacent to the metal/film interface, and an outer layer containing incorporated PO₄³⁻ anions. The total amount and depth of incorporated phosphorus species increase with increasing current density and decreasing temperature, in correspondence with the enhancement of the electric field. The formation conditions for the films include those relevant to the commercial anodising of tantalum for capacitors for which the extent of phosphorus incorporation is shown to be comparatively low.     

In situ scanning tunneling microscopy study of selective dissolution of Au3Cu and Cu3Au (0 0 1)

We present an electrochemical study of Au₃Cu (0 0 1) single crystal surfaces in 0.1 mol dm⁻³ H₂SO₄ and 0.1 mol dm⁻³ H₂SO₄ + 0.1 mmol dm⁻³ HCl, and of Cu₃Au (0 0 1) in 0.1 mol dm⁻³ H₂SO₄. The focus is on in situ scanning tunneling microscopy experiments. The changes of the surface morphology, which are time- and potential-dependent, have been observed, clearly resolving single atomic steps and mono-atomic islands and pits. Chloride additives enhance the surface diffusion and respective morphologies are observed earlier. All surfaces have shown considerable roughening already in the passive region far below the critical potential.