Electrodegradation of the Acid Green 28 dye using Ti/ß-PbO2 and Ti-Pt/ß-PbO2 anodes.

The statistical Response Surface Methodology (RSM) is applied to investigate the effect of different parameters (current density, j, NaCl concentration, [NaCl], pH, and temperature, θ) and their interactions on the electrochemical degradation of the Acid Green (AG) 28 dye using a Ti/ß-PbO2 or Ti-Pt/ß-PbO2 anode in a filter-press reactor. LC/MS is employed to identify intermediate compounds. For both anodes, the best experimental conditions are j = 50 mA cm(-2), [NaCl] = 1.5 g L(-1), pH = 5, and θ = 25 °C. After 3 h of electrolysis, a dye solution treated under these conditions presents the following parameters: electric charge per unit volume of the electrolyzed solution required for 90% decolorization (Q(90)) of 0.34-0.37 A h L(-1), %COD removal of ∼100%, specific energy consumption of 18-20 kW h m(-3), and %TOC removal of 32-33%. No loss of the ß-PbO2 film is observed during all the experiments. The ß-PbO2 films present excellent stability for solutions with pH ≥ 5 ([Pb(2+)] < 0.5 mg L(-1)). Chloroform is the only volatile organic halo compound present in the treated solution under those optimized conditions. Hydroxylated anthraquinone derivatives, aromatic chloramines, and naphthoquinones are formed during the electrolyses. The Ti/ß-PbO2 and Ti-Pt/ß-PbO2 anodes show significantly better performance than a commercial DSA anode for the electrochemical degradation of the AG 28 dye. The Ti/ß-PbO2 anode, prepared as described in this work, is an excellent option for the treatment of textile effluents because of its low cost of fabrication and good performance.

Preparation and characterization of biomimetically and electrochemically deposited hydroxyapatite coatings on micro-arc oxidized Ti-13Nb-13Zr.

Surface properties and corrosion resistance analyses of Ti-13Nb-13Zr coated by an oxide film (obtained by micro-arc oxidation at 300 V) or an oxide/hydroxyapatite (HA) film are reported. HA films were biomimetically or electrochemically deposited on the alloy/oxide surface, and their properties compared. Both the biomimetic and the electrochemical method yielded rough and globular apatite surfaces (10-20 µm globules for the former and 1-2 µm for the latter). As inferred from XRD data, the electrochemical method yielded more biologic-like HA films, while the biomimetic method yielded films containing a mixture of calcium phosphate phases. Coated Ti-13Nb-13Zr samples were immersed in an aerated PBS solution and continuously analyzed during 49 days. Considering that, after immersion, the biomimetically deposited films presented smaller variations in thickness and morphology and higher electric resistance (determined by electrochemical impedance spectroscopy), they clearly provide significantly better protection to the Ti-13Nb-13Zr alloy when in PBS solution.

Influence of hydroxyapatite on the corrosion resistance of the Ti-13Nb-13Zr alloy.

Electrochemical analyses on the biocompatible alloy Ti-13Nb-13Zr wt% in an electrolyte simulating physiological medium (PBS solution) are reported. Hydroxyapatite (HA) films were obtained on the alloy by electrodeposition at constant cathodic current. Samples of the alloy covered with an anodic-oxide film or an anodic-oxide/HA film were analyzed by open circuit potential and electrochemical impedance spectroscopy measurements during 180 days in the PBS electrolyte. Analyses of the open-circuit potential (E (oc)) values indicated that the oxide/HA film presents better protection characteristics than the oxide only. This behavior was corroborated by the higher film resistances obtained from impedance data, indicating that, besides improving the alloy osteointegration, the hydroxyapatite film may also increase the corrosion protection of the biomaterial.

Degradation of phenol using Co- and Co,F-doped PbO(2) anodes in electrochemical filter-press cells.

A comparative study on the electrooxidation of phenol in H(2)SO(4) medium using pure PbO(2) or F-, Co- and Co,F-doped PbO(2) electrodes in filter-press cells was carried out. The oxide films were obtained by galvanostatic electrodeposition using an electrolytic bath containing sodium lauryl sulfate as additive and Pb(2+), F(-), Co(2+) or Co(2+)+F(-), under magnetic stirring (to obtain 4-cm(2) electrodes) or ultrasound waves (to obtain 63-cm(2) electrodes). The best results were attained with PbO(2) electrodes doped with a low-Co content (1mM Co(2+) in the electrolytic bath) along with F(-): the chemical oxygen demand (COD) and the total organic carbon content (TOC) of the simulated wastewaters were removed by about 75% and 50%, respectively. When pure PbO(2) electrodes were used, the COD and TOC removals were about 60% and 45%, respectively. For the smaller electrodes, an average current efficiency (ACE) and an energy consumption (EC) of about 16% and 70 kWh kg(COD)(-1), respectively, were obtained. For the larger electrodes, the ACE and EC values were about 18% and 105 kWh kg(COD)(-1), respectively. Stability tests of the electrodes showed that they are suitable for use in the electrochemical treatment of phenol wastewaters.

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater.

The electrochemical performance of pure Ti-Pt/beta-PbO2 electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l(-1)) was carried out under the following conditions: current density of 50 mA cm(-2), volume flow rate of 2.4 l h(-1), temperature of 25 degrees C and electrode area of 5 cm2. The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l(-1) (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti-Pt/beta-PbO2-Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe3+ and 30 mM F-. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure beta-PbO2 and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.

Electrochemical studies on zirconium and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in simulated physiologic media.

Different electrochemical studies were carried out for Zr and its biocompatible alloys Ti-50Zr at.% and Zr-2.5Nb wt.% in solutions simulating physiologic media, Ringer and PBS (phosphate buffered saline) solutions. The results from rest-potential measurements showed that the three materials are spontaneously passivated in both solutions and that the Ti-50Zr alloy has the greatest tendency for spontaneous oxide formation. Some corrosion parameters (such as the pitting and repassivation potentials) were obtained via cyclic voltammetry in both solutions, revealing that the Ti-50Zr has the best corrosion protection while Zr has the worst. On the other hand, the pre-anodization (up to 8 V vs. SCE) of the alloys in a 0.15 mol/L Na2SO4 solution led to a significant improvement in their protection against pitting corrosion when exposed to the Ringer solution. Elemental analyses by EDX showed that during pitting corrosion, there is no preferential corrosion of any of the alloying elements (Zr, Ti, Nb).

Growth of aluminum-free porous oxide layers on titanium and its alloys Ti-6Al-4V and Ti-6Al-7Nb by micro-arc oxidation.

The growth of oxides on the surfaces of pure Ti and two of its ternary alloys, Ti-6Al-4V and Ti-6Al-7Nb, by micro-arc oxidation (MAO) in a pH 5 phosphate buffer was investigated. The primary aim was to form thick, porous, and aluminum-free oxide layers, because these characteristics favor bonding between bone and metal when the latter is implanted in the human body. On Ti, Ti-6Al-4 V, and Ti-6Al-7Nb, the oxides exhibited breakdown potentials of about 200 V, 130 V, and 140 V, respectively, indicating that the oxide formed on the pure metal is the most stable. The use of the MAO procedure led to the formation of highly porous oxides, with a uniform distribution of pores; the pores varied in size, depending on the anodizing applied voltage and time. Irrespective of the material being anodized, Raman analyses allowed us to determine that the oxide films consisted mainly of the anatase phase of TiO2, and XPS results indicated that this oxide is free of Al and any other alloying element.

Electrochemical degradation of a real textile effluent using boron-doped diamond or ß-PbO2 as anode.

Constant current electrolyses are carried out in a filter-press reactor using a boron-doped diamond (Nb/BDD) or a Ti-Pt/ß-PbO(2) anode, varying current density (j) and temperature. The degradation of the real textile effluent is followed by its decolorization and chemical oxygen demand (COD) abatement. The effect of adding NaCl (1.5 g L(-1)) on the degradation of the effluent is also investigated. The Nb/BDD anode yields much higher decolorization (attaining the DFZ limit) and COD-abatement rates than the Ti-Pt/ß-PbO(2) anode, at any experimental condition. The best conditions are j = 5 mA cm(-2) and 55 °C, for the system's optimized hydrodynamic conditions. The addition of chloride ions significantly increases the decolorization rate; thus a decrease of more than 90% of the effluent relative absorbance is attained using an applied electric charge per unit volume of the electrolyzed effluent (Q(ap)) of only about 2 kA h m(-3). Practically total abatement of the effluent COD is attained with the Nb/BDD anode using a Q(ap) value of only 7 kA h m(-3), with an energy consumption of about 30 kW h m(-3). This result allows to conclude that the Nb/BDD electrode might be an excellent option for the remediation of textile effluents.