Energy harvesting by waste acid/base neutralization via bipolar membrane reverse electrodialysis

Bipolar Membrane Reverse Electrodialysis (BMRED) can be used to produce electricity exploiting acid-base neutralization, thus representing a valuable route in reusing waste streams. The present work investigates the performance of a lab-scale BMRED module under several operating conditions. By feeding the stack with 1 M HCl and NaOH streams, a maximum power density of ~17 W m−2 was obtained at 100 A m−2 with a 10-triplet stack with a flow velocity of 1 cm s−1, while an energy density of ~10 kWh m−3 acid could be extracted by a complete neutralization. Parasitic currents along feed and drain manifolds significantly affected the performance of the stack when equipped with a higher number of t…

Physico-chemical characterization of passive films on 316L stainless steel grown in high temperature water

Enhancing Biocompatibility and Antibacterial Activity of Ti6Al4V by Entrapping Ag and Hydroxyapatite Inside Alginate Filled Pores of TiO 2 Layer Grown by Spark Anodizing

A three-step electrochemical process is developed to grow a coating on Ti6Al4V alloy for biomedical applications aimed to enhance its bioactivity. The coating is composed by a porous titanium oxide filled with Ag, alginic acid, and hydroxyapatite to provide antibacterial properties and, at the same time, osteointegration capability. Anodized and treated with the electrochemical process samples are characterized by Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Spectroscopy (EDX), X-Ray Diffraction, and Raman Spectroscopy to have information about morphology and composition soon after the fabrication and after immersion in Hanks' solution. Bioactivity of the samples is also prov…

Electrochemical synthesis and physico-chemical characterization of CdSe nanotubes

Synergistic Use of Electrochemical Impedance Spectroscopy and Photoelectrochemical Measurements for Studying Solid State Properties of Anodic HfO2

Within the past years, intense research has been carried out on HfO2 as high k material, promising candidate to replace SiO2 as gate dielectric in CMOS based devices (1), and as metal oxide for resistive random access memory (ReRAM) (2). For both technological applications compact, uniform and flat oxides are necessary, and a detailed understanding of their physical properties as a function of the fabrication conditions is strongly. Hafnia performance can be significantly influenced by carrier trapping taking place at pre-existing precursors states (induced by oxygen vacancies, interstitial ions, impurities acting as dopants), or by self-trapping in a perfect lattice, where the potential we…

Electrochemically prepared oxides for resistive switching devices

Redox-based resistive switching memories (ReRAM) based on metal oxides are considered as the next generation non-volatile memories and building units for neuromorphic computing. Using different deposition techniques results however in different structural and electric properties, modulating the device performance. In this study HfO2 and Nb2O5 were prepared electrochemically by anodizing sputtering-deposited Hf and Nb in borate buffer solution. Photoelectrochemical measurements were used to study the solid state properties of the anodic oxides, such as band gap and flat band potential. In the case of anodic HfO2, detected photocurrent is ascribed to optical transitions between localized (gen…

Photocatalytic and photoelectrocatalytic H2 evolution combined with valuable furfural production

In this work the photocatalytic (PC) and photoelectrocatalytic (PEC) reforming of furfuryl alcohol (FA) under environmental friendly conditions was investigated. Both H2 evolution and partial oxidation to furfuraldehyde were followed. For the first time TiO2 based photocatalysts were studied and the photocatalytic activity of home prepared photocatalysts was compared with that of commercial ones under both UVA and simulated solar irradiation. PEC tests were performed by using home prepared TiO2 nanotubes (TiO2 NTs) as photoanode and Pt free Ni foam as cathode to improve the Hydrogen Evolution Reaction (HER). Both the partial FA oxidation reaction rate and H2 evolution rate were normalized f…

Growth and Characterization of Anodic Films on Al-Nb Alloys

Abstract The anodizing behaviours of sputtering-deposited aluminium, niobium and Al-Nb alloys, containing 0.4, 7.5, 21, 40 and 55 at.% niobium, have been examined in 0.1 M ammonium pentaborate electrolyte with interest in the morphology, structure and electronic properties of the anodic oxides. Transmission electron microscopy revealed amorphous oxides, containing units of Nb2O5 and Al2O3, with formation ratios intermediate between those of anodic alumina and anodic niobia. Photocurrent spectroscopy provided increased understanding of the electronic properties of the anodic films, suggesting the formation of “mixed oxides” with insulating behaviours. The estimated band gap values are correl…

Photocurrent Spectroscopy in Corrosion and Passivity Studies. A Critical Assessment

Photocurrent Spectroscopy (PCS) is currently employed for the characterization of solid-state properties of semiconducting and insulating materials, since the knowledge of their band gap is a prerequisite to any possible application in different fields such as: solar energy conversion (photoelectrochemical and photovoltaic solar cells, photocatalysis) and microelectronics (high-k, high band-gap materials) (1-2). In the last 20-30 years an increasing number of scientists working in the area of corrosion has been attracted by this technique owing to its versatility and ability to scrutinize in situ corrosion layers and passive films having semiconducting or insulating behaviour. In previous w…

A photoelectrochemical investigation of conversion coatings on Mg substrates

Abstract The structure, morphology and composition of conversion coatings grown in stannate bath on pure Mg were studied using potential–time, polarization curves, X-ray diffraction, scanning electron microscopy and photocurrent spectroscopy. The coating is manly constituted by crystalline magnesium–tin hydroxide, whose morphology and distribution depends on the conversion bath composition and temperature. The photoelectrochemical investigation allowed to estimate the band gap value of MgSn(OH) 6 and flat band potential. A sketch of the metal/passive film/electrolyte junction formed during conversion on the metal substrate is reported to account for the overall photoelectrochemical behaviou…

Fuel Cell Performances of Bio-Membranes Made of Chitosan-Polyelectrolyte Thin Films and Nanowires into Anodic Alumina Membranes

Chitosan (CS) / Phosphotungstic acid (PTA) polyelectrolytes in the shape of thin films and nanowires supported by Anodic Alumina Membranes (AAM) have been fabricated through solution cast and filtration techniques, respectively. Their ability to function in a H2/O2 fuel cell under mild conditions (room temperature, low humidity and low Pt loading) is proved for the first time. The fabricated membrane electrode assemblies produce power peaks of ~20 mW cm-2 for both films and nanowires. The CS/PTA films (20-40 μm thick) are able to produce a quite constant power density of ~10 mW cm-2 recorded for at least 7 h. The gradual decrease of the power output with time observed for CS/PTA nanowires i…

Photoelectrochemical Characterization of Oxide Layers on 316L Stainless Steel Grown in High temperature Water

Kinetic of growth and physico-chemical characterization of anodic films on magnesium

Fabrication of Bismuth Absorber Arrays for NTD-Ge Hard X-ray Microcalorimeters

The high-spectral-resolution detection of hard X-rays (E > 20 keV) is a challenging and nearly unexplored area in space astrophysics. Traditionally hard X-ray detectors present moderate spectral resolutions, although few tens of eV one could open new frontiers in the study of nuclear processes and high-temperature plasma dynamics in energetic processes. This can be achieved by using cryogenic microcalorimeters. Within a research activity aimed at developing arrays of neutron transmutation-doped germanium (NTD-Ge) microcalorimeters for the high-spectral-resolution detection (about 50 eV@60 keV) of hard X-rays (20 keV < E<100 keV), we developed an electroplating process to fabricate …

Photoelectrochemical evidence of Nitrogen Incorporation during Anodizing of valve metals alloys

Amorphous and/or nanocrystalline oxide films can be easily prepared electrochemically by anodizing. The anodizing allows to grow oxides with structural and compositional features easily and strictly controlled by the process parameters.

Anodic alumina membranes as template for the synthesis of 1-D metal oxide and hydroxide nanostructures

Anodic alumina membranes with highly ordered cylindrical pores and tuneable geometry have been prepared (pore diameters=20−200 nm; pore density 1012-1014 pores/m2; thickness: 20-100 mm) by controlling the anodizing process of aluminum in phosphoric, oxalic and sulphuric acid. The influence of different parameters (initial treatment of aluminium surface, composition of electrolyte, temperature and applied potential) on the final characteristics of the membranes have been investigated. The use anodic alumina membranes as template for the electrosynthesis of some metal hydroxides and oxides 1-D nanostructures (nanowires and nanotubes) will be also proved.

Identification of passive layers on Co in Alkaline solutions by photocurrent spectroscopy

The photoelectrochemical behavior of passive films on Co has been studied as a function of the polarizing voltage and electrolyte composition. Passive layers formed at 0 V (standard hydrogen electrode, SHE) in 0.1 M NaOH consisted of Co(OH) 2 , whose bandgap value has been found to be 1.85 eV. Higher bandgap values (2.75 eV) have been measured for passive films formed in borate buffer at 0 V (SHE), which are mainly consist of CoO. The Eg values have been related to the film composition on the basis of a correlation between the bandgap of passive films and the electronegativity of their constituents.

The Influence of Surface Treatment on the Kinetic of Growth of Anodic Films on Magnesium in Alkaline Solution

Structural and Photoelectrochemical Characterization of Porous Anodic Films on Iron

Use of Mott-Schottky Plots to Characterise the Amorphous Passive Film/Electrolyte Junction

Poster: Polar Dielectrics, Optics, and Ionics

Methanol and proton transport through chitosan-phosphotungstic acid membranes for direct methanol fuel cell

Composite chitosan-phosphotungstic acid membranes were synthesized by ionotropic gelation. Their liquid uptake is higher for thin membranes (23 ± 2 μm), while it is lower (~70%) for thicker membranes (50-70 μm). Polarization curves recorded using single module fuel cell at 70°C allowed to estimate a peak power density of 60 mW cm−2 by using 1 M as methanol and low Pt and Pt/Ru loadings (0.5 and 3 mg cm−2) at the cathode and at the anode, respectively. Electrochemical impedance spectroscopy was used to estimate the membrane conductivity and to model the electrochemical behavior of methanol electrooxidation inside the fuel cell revealing a two-step mechanism mainly responsible of overall kine…

The Effect of Nb Incorporation on the Electronic Properties of Anodic HfO2

Hafnium oxide and Nb doped HfO2 were grown by anodizing sputtering-deposited Hf and Hf-4at.%Nb. Photoelectrochemical characterization was carried out in order to estimate solid state properties such as band gap, flat band potential and electrons internal photoemission threshold energy as a function of thickness and composition of anodic oxides. Optical transitions at energy lower than the band gap value of the investigated anodic films were evidenced, and they are attributed to optical transitions involving localized states inside the band gap. Such states were located at 3.6 eV and 3.9 eV below the conduction band edge for the Nb free and Nb containing hafnium oxide, respectively. Impedanc…

Light induced electropolymerization of poly(3,4-ethylenedioxythiophene) on niobium oxide

Abstract The photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered niobium. Photocurrent Spectroscopy was employed to study the optical properties of Nb/Nb 2 O 5 /PEDOT/electrolyte interface in a large range of potential, and to get an estimate of the band gap and flat band potential of both the oxide and the polymer. Scanning Electron Microscopy was used to study the morphology of PEDOT. Both the optical and morphological features of the photoelectrochemically grown polymer were compared with those showed by PEDOT electropolymerized on gold conducting substrate.

Electronic properties and corrosion resistance of passive films on austenitic and duplex stainless steels

Abstract Passive films were grown at constant potential in acidic (pH∼2) and alkaline (pH∼13) solutions on chromium, AISI 304L, AISI 316L and Duplex stainless steels. Passive films on chromium grow following a high field mechanism considering the presence of dissolution phenomena. According to the photoelectrochemical characterization, passive films on Cr have a bandgap of 3.4 eV when formed in acidic solution, and of 2.4 eV when formed in alkaline solution due to the formation of Cr(OH)3. These films result to be poorly stable against anodic dissolution due to a very anodic flat band potential. Conversely, impedance and photoelectrochemical measurements proved that passive films on stainle…

Redshift of absorption threshold of TiO2 Nanotubes due to Cu2O electrodeposition

Qualitative Models for the Photoresponse and Capacitance of Annealed Titania Nanotubes

Physicochemical characterization of annealed TiO2 nanotubes (TNTs) was conducted by using photocurrent spectroscopy and differential capacitance techniques. It has been shown that the geometry and architecture of nanotubes determine how photogenerated electrons and holes are separated and transferred. Photocurrent generation in TNTs is a consequence of two phenomena; drifting of holes into the electrolyte and diffusion of electrons toward the substrate. These two processes have been shown to be independent of the anodic polarization. The capacitance of TiO2 nanotubes is also affected by their geometry. In anodic potentials, with respect to the flat band potential of the underlying barrier l…

The Effect of Anodizing Bath Composition on the Electronic Properties of Anodic Ta-Nb Mixed Oxides

Anodic oxides were grown to 50 V on Ta-Nb sputtering deposited alloys, with high Nb content, in acetate ions containing an aqueous solution to study the effect of the anodizing bath composition on anodic layers’ dielectric properties. Photoelectrochemical measurements proved the presence of a photocurrent in the band gap of photon energy lower than oxides, due to optical transitions involving localized electronic states as a consequence of acetate ions incorporation. Flat band potential value estimates assessed the insulating nature of the anodic oxides grown in the acetate buffer solution. Differential capacitance measurements showed that the highest capacitance value was measured for the …

Physico-chemical characterization of anodic films on sputter-deposited Al-Nb alloys.

The influence of surface treatment on the anodizing of Magnesium in Alkaline Solution

Photocurrent spectroscopy of thin passive films

Publisher Summary This chapter reviews theoretical background on the photoelectrochemistry of metal and semiconductor electrodes on which photocurrent spectroscopy (PCS) relies, by focusing particularly on new features that are typical of the photoelectrochemical behavior of thin passive films and usually absent in the behavior of bulk crystalline semiconductors. The chapter also highlights the advantages of PCS in getting in situ information on the structure of the metal-passive-film-electrolyte systems and shows a more recent quantitative use of this technique in characterizing the composition of passive films. The formation of a protective film on a metallic surface is a key step in esta…

Electronic Properties of Thermal Oxides on Ti and Their Influence on Impedance and Photoelectrochemical Behavior of TiO2 Nanotubes

Thermal oxidation of titaniumwas carried out at 350◦C, 450◦C, and 550◦C for 2 h or 12 h.X-rayDiffraction and Raman Spectroscopy suggest that the thermal oxides are scarcely crystallinewhen the annealing temperature is low, while both anatase and rutile are present for high annealing temperature and time. Photoelectrochemical measurements allowed estimation of a bandgap decreasing from 3.35 eV to 3.15 eV with increasing annealing temperature. The impedance spectra confirmed the formation of n-type semiconductors, with an impedance strongly decreasing on going from a reverse bias toward a forward bias regime. TiO2 nanotubes grown by anodizing Ti in NH4F and water containing ethylene glycol so…

Phosphomolybdic acid and mixed phosphotungstic/phosphomolybdic acid chitosan membranes as polymer electrolyte for H2/O2 fuel cells

Abstract Flat, free-standing phosphomolybdic acid and mixed phosphotungstic/phosphomolybdic acid chitosan membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by heteropolyacid. Scanning electron microscopy revealed the formation of compact and homogenous polymeric membranes, whose thickness resulted to be dependent on reticulation time, and almost independent on the employed heteropolyacid nature and concentration. X-ray diffraction and Fourier transform infrared spectroscopy evidenced the formation of crystalline membranes without appreciable concentration of unprotonated NH 2 groups and heteropolyacid ions with p…

Electronic properties and mobile defects distribution in amorphous semiconducting passive films

A study of the electronic properties of thin (drop 25 nm) a-WO3 and a-Nb2O5 is presented. Based on theory of amorphous semiconductor Schottky barrier the fitting of admittance curves in a large range of electrode potential (around 9 V) and a.c. frequency (100 Hz - 10 kHz) is performed. A density of electronic state distribution (DOS) is derived, which mimics the mobile defects distribution suggested by the classical high field model of oxides growth.

Heterogeneous photocatalytic aqueous succinic acid formation from maleic acid reduction

This study reports the anaerobic reduction of maleic acid to succinic acid in aqueous dispersion of different TiO2 based photocatalysts. Some home prepared and commercial solids containing different polymorphic phases of TiO2 and loaded with Pt and Ru were compared at different acidic pHs. The aim of the work was to verify the feasibility of the process and to determine the best samples and the optimal experimental conditions of the reaction. The best selectivity towards succinic acid was 23.2 % at 70 % of maleic acid conversion. Fumaric acid was also formed as another high added value compound, and its quantity was related to the experimental conditions and the photocatalyst used.

Monitoring of Rouging and De-Rouging of Stainless Steel for Chemical Reactors by Photoelectrochemical and Impedance Measurements

The food and fine-chemical industry has for a long time been troubled by red brown to dark violet deposits in distillation columns, storage vessels and distribution systems for purified water and clean steam. Owing to the visual appearance of those deposits, the phenomena was referred as rouge. Although formation of rouge, i.e. rouging, is a commonly known phenomenon in stainless steel systems, the basic mechanism is still not fully understood. The phenomenon causes precipitation of iron as fine red-brown ferric oxide or hydroxide particles. Moreover adherent discoloration of the stainless steel surface is often observed in conjunction with the loosely adhered rouge particles. The affected …

Influences of structure and composition on the photoelectrochemical behaviour of anodic films on Ti-Zr alloys

Effect of E. coli biofilm formation and removal on passive films on AISI 316L during fermentation processes

Abstract 316L coupons were sanitized in hot water vapour inducing iron enrichment in passive films. Coupons were then immersed in a pilot fed-batch fermenter in presence of E. coli. Sanitization causes iron enrichment in passive films. Fermentation causes the growth of biofilm on the SS, constituted by bacteria embedded in an extracellular polymeric substance. During fermentation SS open circuit potential is very negative due to low oxygen concentration on its surface, while the chelating action of siderophores induces chromium enrichment in the passive film. Disinfection in NaClO for 30 min allows removal of biofilm and formation of a protective passive film.

Red Shift in the Light Absorption Threshold of Anodic TiO2 Films Induced by Nitrogen Incorporation

Abstract Titanium foils were anodized in ammonium containing and ammonium free solutions in order to check the possibility of inducing nitrogen incorporation into anodic TiO 2 films. XPS spectra confirmed the presence of O-Ti-N bonds on the surface of the anodic films prepared in ammonium biborate electrolytes. In order to evidence the effect of nitrogen incorporation on the light absorption threshold, photoelectrochemical behavior of as-anodized and high temperature annealed films as a function of the anodizing electrolyte composition were investigated. A photocurrent tail at energies lower than the mobility gap of TiO 2 appeared for those films prepared in ammonium containing electrolytes…

Corrosion of stainless steel in food and pharmaceutical industry

Abstract Stainless steels are widely used in the food and pharmaceutical industry because of their high corrosion resistance and superior mechanical properties. These features are crucial because produced foodstuffs and drugs must comply with high purity and quality standards. Just a proper selection of stainless steel grade can prevent corrosion phenomena that can be detrimental to the whole manufacturing process. Food/drugs production process phases will be here analyzed and discussed with a particular emphasis on the possible corrosion mechanism of stainless steels in those particular operating conditions. Recent advances on the methods to assess corrosion of stainless steels in food and…

Semiconductor electrochemistry approach to passivity and passivity breakdown of metals and metallic alloys

AbstractA critical appraisal of the use of the theory of semiconductors in characterising passive films on metals and alloys is provided, with special emphasis on the use of Mott-Schottky theory for the location of characteristic energy levels of the passive film-electrolyte junction. Some inconsistencies between theory and experimental results in the case of thin passive films are discussed together with possible alternative ways for overcoming such problems. The role of semiconducting properties in determining the pitting behaviour of passive films on W in solutions containing halide is presented and discussed. The validity of a recently proposed correlation between the solid state proper…

Electrodeposition and physico-chemical characterisation of Fe, Ti and mixed Fe/Ti oxides nanotubes

Electrochemically prepared oxides for resistive switching memories

Redox-based resistive switching memories (ReRAMs) are the strongest candidates for next generation nonvolatile memories. These devices are commonly composed of metal/solid electrolyte/metal junctions, where the solid electrolyte is usually an oxide layer. A key aspect in the ReRAMs development is the solid electrolyte engineering, since it is crucial to tailor the material properties for obtaining excellent switching properties (e.g. retention, endurance, etc.). Here we present an anodizing process as a non vacuum and low temperature electrochemical technique for growing oxides with tailored structural and electronic properties. The effect of the anodizing conditions on the solid state prop…

Physicochemical characterization and photoelectrochemical analysis of iron oxide films

Iron oxide films with a nanoporous structure were grown by anodizing sputter-deposited Fe in a fluoride containing ethylene glycol solution and annealed under air exposure at different temperatures. X-ray diffraction and Raman spectroscopy allowed to identify the presence of hematite and/or magnetite after thermal treatment for films annealed at T ≥ 400 °C under air exposure. According to GDOES compositional depth profiles, the thermal treatment sensitively reduced the amount of fluoride species incorporated into the film during the anodizing process. A band gap value of ~2.0 eV was estimated for all the investigated layers, while a flat band potential dependent on both the growth condition…

Role of Molybdenum on the Electronic Properties of Passive Films on Stainless Steels

Potentiostatic polarization of different stainless steel grades with a mirror surface finishing was performed in order to investigate the role of Mo on stainless steels corrosion behaviour. In the attempt to gain more insight into transpassive dissolution mechanism, passive films were grown in neutral aqueous solution (pH ∼ 7) at different polarizing potentials ranging from passive to transpassive conditions. According to the photoelectrochemical characterization, Cr dissolution occurs even at low polarizing potentials in the case of AISI 304L, while higher band gap values were obtained for passive films grown on austenitic 316L and duplex SSs. Capacitance measurements suggest that the flat…

Semiconducting properties of passive films and corrosion layers on weathering steel

Abstract Anodic films were grown on Weathering Steel by potentiostatic polarization in slightly alkaline solution. The photoelectrochemical results reveal that they are n-type iron oxide with Eg = 2.0 eV. Rust layer grown by atmospheric corrosion are n-type semiconductors with a band gap higher than that estimated for the anodic film attributed to the formation of γ-lepidocrocite. The electrochemical impedance spectra allow to evidence that rust layers have a higher conductivity with respect to anodic films due to the presence of highly doped iron oxide layers. The use of Mott-Schottky theory to model the dependence of oxide capacitance as function of potential is critically discussed.

Erroneous p-type assignment by Hall effect measurements in annealed ZnO films grown on InP substrate

We report on incorrect carrier type identification achieved by Hall effect measurements performed on ZnO films grown by pulsed laser deposition on InP substrates and subsequently annealed for 1 h at 600 C in air. While Hall measurements, after post-growth annealing, reveal a change in the electrical properties of the films, from n-type to p-type, both photocurrent-based and standard C V measurements performed on the same samples show no change in the native n-type doping of the ZnO films. A possible interpretation of the two results is reported. In particular, p-type conductivity observed by Hall effect may be ascribed to a highly conductive thin layer formed during the annealing process at…

Heteropolyacids - Chitosan Membranes for H2/O2 Low Temperature Fuel Cells

Proton exchange membrane fuel cells (PEMFCs) have received much attention in recent years because of their high power density, efficiency and zero-environmental pollution. As one of the key components in fuel cells, the proton exchange membrane is expected to have high proton conductivity and good electrochemical stability. In the attempt to promote PEMCFs commercialization, high cost of fuel cell systems and short lifecycle are the two main issues that need to be addressed, thus large research effort has been devoted in developing new polymer electrolytes that can replace the usually employed proton conductors, e.g. Nafion®, with other membranes of comparable performances but lower cost.A…

Electrochemically-induced TiO2 incorporation for enhancing corrosion and tribocorrosion resistance of PEO coating on 7075 Al alloy

Abstract 7075 Al alloy was PEO-treated in a silicate based electrolyte containing 3 g l-1 potassium titanyl oxalate using unipolar and bipolar pulsed current waveforms. The coating formed by the bipolar waveform with the wider cathodic pulses showed volcano-like surface morphology with no evidence of large pores at the metal/coating interface. It revealed the highest corrosion performance due to the synergistic effect of TiO2 incorporation and structural/morphological features along with a better passivation behavior indicating no pitting susceptibility. For this coating, the tribocorrosion tests showed no potential drop during sliding under 1 N with the lowest volume loss of 0.022 mm3.

Photoelectrochemical monitoring of rouging and de-rouging process on AISI 316L for chemical reactors

The food and fine-chemical industry has for a long time been troubled by red brown to dark violet deposits in distillation columns, storage vessels and distribution systems for purified water and clean steam. Owing to the visual appearance of those deposits, the phenomena was referred as rouge. Although formation of rouge, i.e. rouging, is a commonly known phenomenon in stainless steel systems, the basic mechanism is still not fully understood. The phenomenon causes precipitation of iron as fine red-brown ferric oxide or hydroxide particles. Moreover adherent discoloration of the stainless steel surface is often observed in conjunction with the loosely adhered rouge particles. The affected …

Structural Analysis and Photocurrent Spectroscopy of CCCs on 99.99% Aluminum

A characterization of chromate conversion coatings (CCCs) formed in the presence and in the absence of accelerator (ferroferricyanide redox couple) has been performed by various techniques (transmission electron microscopy, TEM, glow discharge optical emission spectrometry, GDOES, X-ray absorption near-end structure, XANES, and photon correlation spectroscopy). The results of a detailed investigation on morphological, compositional, and solid-state properties of freshly converted aluminum samples at different immersion times (30 s-90 min) are reported. The TEM and GDOES data suggest the presence of iron-cyanide species only in the external layer of CCC of nearly constant thickness. The XANE…

Highly Active and Stable NiCuMo Electrocatalyst Supported on 304 Stainless Steel Porous Transport Layer for Hydrogen Evolution in Alkaline Water Electrolyzer

Several functionalized porous transport layers with Pt-free electrocatalysts for hydrogen evolution reaction in alkaline conditions, based on Ni, Cu, and Mo, are prepared through electrodeposition onto a 304 stainless steel mesh. Morphological characterization confirms the fabrication of electrodes with high electrochemical surface active area due to the formation of hierarchical nanostructures. Mo presence into the electrocatalysts increases the activity toward the hydrogen evolution reaction. The optimization of electrodeposition process leads to the preparation of highly active NiCuMo electrocatalyst that exhibits near zero onset overpotential and overpotentials of 15 and 113 mV at 10 an…

Synergistic effect of W incorporation and pulsed current mode on wear and tribocorrosion resistance of coatings grown by plasma electrolytic oxidation on 7075 Al alloy

Ceramic coatings were grown by plasma electrolytic oxidation on 7075 Al alloy using unipolar and bipolar pulsed current waveforms with 20 and 40% cathodic duty cycles, from a silicate-based bath without and with the addition of Na2WO4. Pancake-like morphology was dominant on the coatings grown by unipolar waveform, while the bipolar waveforms promoted volcano-like morphology, increased the roughness of the coating surface and the formation of more compact layers. The coatings produced using the bipolar waveforms provided higher resistances toward both tribocorrosion and dry sliding conditions, while further improvement was achieved by the presence of tungsten. The coatings produced in tungs…

The Influence of Thermal Treatment on the Electronic Properties of a-Nb2O5

The effect of thermal treatments for 1h at 250{degree sign}C in air or under vacuum on the electronic structure of thick amorphous anodic niobia was characterized by electrochemical impedance, differential admittance (DA) and photocurrent spectroscopy (PCS). The analysis of anodized niobia has revealed that it behaves as a pure dielectric. The thermal treatment in air increases the value of the differential capacitance of the niobia sample. The effect is stronger when the thermal treatment is carried out in vacuum and can be cancelled out by reanodizing the oxide to the initial formation potential. In the case of thermally vacuum-treated sample, a behavior typical of semiconducting amorphou…

The influence of composition on band gap and dielectric constant of anodic Al-Ta mixed oxides

Al-Ta mixed oxides were grown by anodizing sputter-deposited Al-Ta alloys of different composition. Photocurrent spectra revealed a band gap, Eg, slightly independent on Ta content and very close to that of anodic Ta2O5 (∼4.3 eV) with the exception of the anodic film on Al-10at% Ta, which resulted to be not photoactive under strong anodic polarization. The photoelectrochemical characterization allowed to estimate also the oxides flat band potential and to get the necessary information to sketch the energetic of the metal/oxide/electrolyte interfaces. Impedance measurements allowed to confirm the formation of insulating material and to estimate the dielectric constant of the oxides, which re…

Photocurrent Spectroscopy Applied to the Characterization of Compositionally and Structurally Graded Materials: from Thin Films to Nanostructures

Characterization of the Solid State Properties of Anodic Oxides on Magnetron Sputtered Ta, Nb and Ta-Nb Alloys

Tantalum oxide, niobium oxide and Ta-Nb containing mixed oxides were grown by anodizing sputter-deposited Ta, Nb and Ta-Nb alloys of different compositions. A photoelectrochemical investigation was performed in order to estimate the band gap and the flat band potential of the oxides as a function of their composition. The band gap of the investigated Ta-Nb containing mixed oxides changed monotonically between those estimated for Ta2O5 (4.1 eV) and Nb2O5 (3.4 eV) and in agreement with a proposed correlation between the Band gap of an oxide and the difference of electronegativity of the oxide constituents. From the differential capacitance curves recorded in a wide range of electrode potentia…

The effect of Annealing Conditions on the Impedance and on the Photoelectrochemical behavior of TiO2 Nanotubes

Titanium oxide nanotubes (NTs) have attracted much attention during last decade due to their special characteristics such as one-dimensional highly ordered geometry with large surface area and good chemical and optical stability.

Photoelectrochemical Characterization of Porous Anodic Films on Iron Grown in Fluoride-containing Ethylebe Glycol Electrolyte

Structural and compositional analysis of anodic films on Al-Nb sputter-deposited alloys

The photoelectrochemical behavior of anodic films on Al alloys, containing titanium, tantalum, and tungsten (valve metals), has been studied as a function of alloy composition and anodizing conditions. Photocurrent spectroscopy has been used to get information on bandgap and the flatband potential values of different mixed oxides. Both insulator-like and semiconducting behavior has been observed for anodic oxides grown on Al-W and Al-Ti alloys dependent on alloy initial composition. Optical bandgap values, Eg,opt, of different oxides are in accordance with predictions based on the correlation between Eg,opt and the difference of electronegativities of the oxide constituents, indicating pote…

Physicochemical characterisation of thermally aged anodic films on magnetron sputtered niobium

The influence of thermal aging, at intermediate temperature (1h at 250°C) and in different environments, on the electronic and solid-state properties of stabilized 160 nm thick amorphous anodic niobia, grown on magnetron sputtered niobium metal, has been studied. A detailed physicochemical characterisation of the a-Nb2O5/0.5M H2SO4 electrolyte junction has been carried out by means of photocurrent and electrochemical impedance spectroscopy as well by differential admittance measurements. A change in the optical band gap (3.45 eV) of niobia film has been observed after aging (3.30 eV) at 250°C in air for 1 hour. A cathodic shift (0.15-0.2 Volt) in the flat band potential of the junction has …

Initial Surface Film on Magnesium Metal. A Characterization by X-ray Photoelectron Spectroscopy (XPS) and Photocurrent Spectroscopy (PCS)

Abstract A detailed investigation of the initial film grown on mechanically polished Mg electrodes has been carried out by ex situ X-ray Photoelectron Spectroscopy (XPS) and in situ Photocurrent Spectroscopy (PCS), allowing to reach a detailed picture of the passive layer structure. The XPS data show that the films formed soon after mechanical treatment and immersion in aqueous electrolyte have a bilayer structure, consisting of an ultra-thin MgO inner layer (∼2.5 nm) and a Mg(OH) 2 external layer. The thickness of the Mg(OH) 2 layer is a function of immersion time and solution temperature. After mechanical treatment and immersion in aqueous solution at room temperature, the MgO/Mg(OH) 2 la…

1D cerium oxy-hydroxide nanostructures deposition via electrogeneration of base into anodic alumina membrane

Electrochemical fabrication of high k Al-Ta mixed oxides

Influence of heteropolyacid in enhancing proton conductivity of chitosan membranes for H2/O2 Fuel Cells

To promote Proton Exchange Membrane Fuel Cells (PEMFCs) commercialization, large research effort has been devoted in developing new polymer electrolytes that can replace the usually employed proton conductors, e.g. Nafion®, with other membranes of comparable performances but lower cost. Chitosan (CS)-based membrane electrolyte is currently studied as alternative candidate for PEMFC application. Several works have shown that Heteropolyacids (HPAs) can be used to prepare Chitosan polyelectrolytes (PECs) to be employed as proton exchange membrane in low temperature fuel cell. In previous works [1-3] we have shown that CS/PTA membranes, prepared using alumina porous medium for the slow release …

Photoelectrochemical and XPS characterisation of oxide layers on 316L stainless steel grown in high-temperature water

Passive films on AISI 316L stainless steel were grown by exposure in high temperature (300 °C and 150 bar) water. X-ray photoelectron spectroscopy was employed to study their composition as a function of immersion time. A photoelectrochemical investigation, supported by electrochemical and impedance measurements, allowed to get information on the solid-state properties of the investigated layers. The experimental results suggest the formation of a stratified layer with an outer iron-rich layer and an inner Cr-rich oxide layer, whose relative thickness and composition are dependent on the immersion time.

Electrochemical fabrication of metal/oxide/conducting polymer junction

After discovery of conducting polymers and the possibility to modify their electrical properties from insulating to metallic like behavior by doping and a careful choice of the processing conditions, a large amount of research effort has been devoted to the theoretical understanding of their solid state properties as well as to exploit the possible application of conducting polymers in many technological fields including large area organic electronics, polymer photovoltaic cell, and sensors. 1-4 Organic thin film transistors appear very promising devices for the development of low cost, flexible, and disposable plastic electronics. In order to reduce the operating voltage it has been sugges…

Photoelectrochemical behaviour of passive layers on Co in alkaline solutions

Performance of H2-fed fuel cell with chitosan/silicotungstic acid membrane as proton conductor

Composite organic–inorganic proton exchange membranes for H2–O2 fuel cells were fabricated by ionotropic gelation process combining a biopolymer (chitosan) with a heteropolyacid (silicotungstic acid). According to scanning electron microscopy analysis, compact, homogeneous and free-standing thin layers were synthesized. X-ray diffraction proved the crystallinity of the fabricated membranes and showed the presence of Chitosan Form I polymorph soon after the reticulation step and of the Form II polymorph after the functionalization step. Fourier-transform infrared spectroscopy demonstrated that the Keggin structure of the heteropolyacid is maintained inside the membrane even after the fabrica…

Photoelectrochemical Techniques in Corrosion Studies

Growth and Characterization of Anodic Films on Magnesium in Alkaline Solution

Physico-Chemical Characterization of Anodic Oxides on Hf as a Function of the Anodizing Conditions

Anodic films were grown to 5 V (Ag/AgCl) on mechanically polished Hf in 0.1 M ammonium biborate and 0.1 M NaOH. Independent of the anodizing conditions, the photoelectrochemical characterization allowed the observation of optical transitions at 3.25 eV, i.e. at photon energy lower than the bandgap of HfO2. They are attributed to localized states inside the gap of the oxide induced by the presence of oxygen vacancies. From the cathodic photocurrent spectra, it was possible to estimate an energy threshold of ∼2.15 eV for internal electron photoemission phenomena. The impedance measurements proved the formation of insulating oxides with ϵ =19. The anodizing occurs under a high field regime wit…

Electrochemical Fabrication of Inorganic/Organic Field Effect Transistor

After discovery of conducting polymers and the possibility to modify their electrical properties (from insulating to metallic-like behaviour) by doping and a careful choice of the processing conditions, a large amount of research effort has been devoted to the theoretical understanding of their solid state properties as well as to exploit the possible application of conducting polymers in many technological fields including: large area organic electronics, polymer photovoltaic cell and sensors (1-2). Organic thin-film transistors appears very promising for the development of low cost, flexible and disposable plastic electronics. In order to reduce the operating voltage it has been suggested…

TiO2 in memristors and resistive random access memory devices

Abstract One of the most recent applications of TiO2 thin films is as an oxide layer in memristors, electronic devices considered as one of the most promising nonvolatile memories and as possible building units for neuromorphic computing. This chapter aims to describe several fabrication ways, either (electro)chemical or physical methods, of TiO2 thin films and to highlight the relationship between method and layer properties. Some fundamentals on the mechanism of memristors’ operation, that is, resistive switching in oxide thin films, will be given, classifying the different types of devices based on the used electrode materials and underlying physicochemical processes. Finally, it will be…

Photocurrent spectroscopy in passivity studies

The aim of this article is to present photocurrent spectroscopy as useful in situ technique for the physicochemical characterization of passive films and corrosion layers. The response of (both amorphous and crystalline) semiconductor/electrolyte junction under irradiation is treated and discussed in order to get information about solid-state properties such as band gap and flat band potential. The possibility to use Photocurrent Spectroscopy (PCS), in a quantitative way, to get information on the composition of corrosion layers is discussed through a semiempirical correlation between the band gap of the oxides (or hydroxides) and the difference of electronegativity of their constituents. F…

A Critical Assessment of Mott-Schottky Analysis for the Characterisation of Passive Film-Electrolyte Junctions

Dual Ni/Ni-Co electrodeposited coatings for improved erosion-corrosion behaviour

Abstract Industrial applications of hydrophobic metallic coatings are limited to durability of their surface structures against detrimental effects of the surrounding environments. In the present research, the life-long of the hierarchical structure of hydrophobic nickel coating in an erosive-corrosive solution was investigated. The effect of alloying with cobalt on strengthening the hierarchical structures was also investigated. In this regard, highly hydrophobic Ni/Ni, Ni-Co/Ni-Co, dual Ni/Ni-Co and dual Ni-Co/Ni coatings with rough hierarchical structures were electrodeposited. In situ electrochemical measurements were performed to investigate changes in corrosion resistance and hydropho…

Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxide Film Composition

A critical assessment of the Photocurrent Spectroscopy (PCS) Technique for the semi-quantitative characterization of passive film and corrosion layers composition is carried out. We take into account more than three decades of PCS usage as "in-situ" analytical technique and related results as well as the criticism of the underlying semi-empirical correlation relating the measured optical bandgap (Eg) to the passive film composition. The discrepancies between the experimental data, gathered by PCS measurements, and Egestimates originating from recently developed Density Functional Theory based modeling of solid state properties are stressed with particular emphasis on the case of anodic pass…

Structural and compositional analysis of anodic films on Al-Nb sputter-deposited alloys

Porous Anodic Alumina as template for the cathodic electrodeposition of oxide and hydroxide nanostructures

Physico-chemical characterization and corrosion properties of friction stir welded Al2024-T4 alloys

Oxide and Hydroxide nanostructures embedded into Anodic alumina membranes prepared by means of electrogeneration of base

Fabrication and characterization of microscale HfO2-based Memristors

Memristors are metal/insulator/metal devices whose resistance can be switched between two different states (i.e. the low resistive state LRS, and the high resistive state, HRS) by applying a proper voltage value over the two metal contacts [1], [2]. Their simple structure makes memristors prone to extreme down scaling and 3-D stacking potentiality, and excellent compatibility with the complementary metal-oxide-semiconductor (CMOS) technology. Moreover, because of their low power consumption and high speed, memristors are rightly considered the elemental bricks for a next generation of high-density nonvolatile memories. HfO2 has attracted much attention as an oxide material for memristor app…

Effect of Composition on the Photoelectrochemical Behavior of Anodic Oxides on Binary Aluminum Alloys

The photoelectrochemical behavior of anodic films on Al alloys, containing titanium, tantalum, and tungsten (valve metals), has been studied as a function of alloy composition and anodizing conditions. Photocurrent spectroscopy has been used to get information on bandgap and the flatband potential values of different mixed oxides. Both insulator-like and semiconducting behavior has been observed for anodic oxides grown on Al-W and Al-Ti alloys dependent on alloy initial composition. Optical bandgap values, E opt g , of different oxides are in accordance with predictions based on the correlation between E opt g and the difference of electronegativities of the oxide constituents, indicating p…

Solid State Properties of Anodic Hf-Nb Mixed Oxides

In last decades, HfO2 and Nb2O5 have been extensively studied due to their many potential applications, from corrosion protection to CMOS (as high-k gate dielectrics) [1-2] and ReRAM technologies [3-4]. For these technological applications compact, uniform and flat oxides are necessary, and a detailed understanding of their physical properties as a function of the fabrication conditions is needful. Scientific community gradually shifted its interest from pure metal oxides to mixed metal oxides trying to exploit the advantages of pure oxides and to suppress their disadvantages. Mixed oxides can be grown on valve metals alloys by anodizing, a simple and low cost electrochemical process for pr…

The corrosion and tribocorrosion resistance of PEO composite coatings containing α-Al2O3 particles on 7075 Al alloy

Abstract Plasma electrolytic oxidation (PEO) of 7075 Al alloy was carried out in silicate base electrolyte containing 200 nm diameter α-Al2O3 particles for producing composite coatings. The process was performed under a soft-sparking regime using a pulsed bipolar signal with several concentrations of α-Al2O3 particles. It was found that the incorporation of α-Al2O3 particles into the coating did not significantly alter the thickness and roughness of the coating. However, the α-Al2O3 particles were detected on surface of the composite coatings. Corrosion tests showed significant improvement in corrosion performance of the composite coatings due to the efficient pore blocking provided by α-Al…

Fabrication and characterization of micrometer-scale ZnO memristors

Memristors are an interesting class of resistive random access memory (RRAM) based on the electrical switching of metal oxide film resistivity . They are characterized for exhibiting resistive switching between a high-resistance state (HRS) and a low-resistance state (LRS) and have been recently considered as one of the most promising candidates for next-generation nonvolatile memory devices because of their low power consumption, fast switching operation, nondestructive readout, and remarkable scalability. The device structure is simply an oxide layer sandwiched between two metal electrodes. The switching behaviour is dependent both on the oxide material and the choice of metal electrodes.…

Cs0.86(NH41.14SO4Te(OH)6 in porous anodic alumina for micro fuel cell applications.

Abstract Cs0.86(NH4)1.14SO4Te(OH)6 supported by anodic alumina membranes (AAMs) has been characterized for the first time in H2/O2 fuel cell. The fabricated membrane electrode assemblies are able to produce peak power densities in the range 15–30 mW cm−2 under mild conditions (room temperature, low humidity and low Pt loading) and show an increased durability with cycling with respect to previous results obtained with AAM-based fuel cell. The physico-chemical characterization of the electrolytes has been carried out through X-ray diffractometry, scanning electron microscopy and micro-raman analysis. An estimation of the composite membranes conductance under fuel cell operation has been carr…

A facile way to synthesize noble metal free TiO2 based catalysts for glycerol photoreforming

In this work anaerobic heterogeneous photocatalytic solar/UV light reforming of glycerol in aqueous media was performed with Pt-photodeposition and noble metal free modified TiO2 photocatalysts prepared through ball milling, a very simple and cheap coupled catalyst preparation method. Different amounts of Cu2O or 3% CuO were loaded on TiO2 using ball milling and during each run glycerol conversion, hydrogen and CO2 formed in the gas phase and 1,3-dihydroxyacetone (DHA) and glyceraldehyde (GA) in the liquid phase were determined. The results were compared with the aim to verify the effectiveness of Cu2O in replacing Pt. Using noble metal free photocatalysts, 33% glycerol conversion, 10.3% an…

Phosphomolybdic Acid and Mixed Phosphotungstic/Phosphomolybdic Acid Chitosan Membranes for H2/O2 Fuel Cells

Proton exchange membrane fuel cells (PEMFCs) have received much attention in recent years because of their high power density, efficiency and zero-environmental pollution. As one of the key components in fuel cells, the proton exchange membrane is expected to have high proton conductivity and good electrochemical stability. In the attempt to promote PEMCFs commercialization, high cost of fuel cell systems and short lifecycle are the two main issues that need to be addressed, thus large research effort has been devoted in developing new polymer electrolytes that can replace the usually employed proton conductors, e.g. Nafion®, with other membranes of comparable performances but lower cost. A…

Tuning of the optical and dielectric properties of anodic film on sputtered deposited Ta-Nb alloys

Photocurrent Spectroscopy in Corrosion and Passivity Studies. A Critical Assessment

Photocurrent Spectroscopy (PCS) is currently employed for the characterization of solid-state properties of semiconducting and insulating materials, since the knowledge of their band gap is a prerequisite to any possible application in different fields such as: solar energy conversion (photoelectrochemical and photovoltaic solar cells, photocatalysis) and microelectronics (high-k, high band-gap materials) (1-2). In the last 20-30 years an increasing number of scientists working in the area of corrosion has been attracted by this technique owing to its versatility and ability to scrutinize in situ corrosion layers and passive films having semiconducting or insulating behaviour. In previous w…

Anodic TiO2 in ReRAM: Influence of Si-doping on the Resistive Switching Properties of Titanium Oxide

TiO2 has attracted much attention due to its potential widespread applications, including capacitors, photocatalysis, solar energy conversion and, more recently, redox-based random access memories (ReRAM). For micro and nano-electronics applications, TiO2 is usually grown through Chemical and Physical Vapour Deposition techniques, such as Atomic Layer Deposition (ALD), Pulsed Laser Deposition (PLD), Sputtering and so on. In ReRAM field, the control of oxide structure (crystallinity, defects concentration etc.) and the choice of electrodes are crucial to have resistive switching phenomena inside the oxide. Thus, anodizing can be proposed as a simple and low cost way to grow TiO2 and to tune …

Photoelectrochemical characterization of conversion coatings and passive films formed on mg in different electrolytes

Effect of ammonium hydroxide addition in the anodizing electrolyte on the electronic properties of anodic oxides on Niobium

Electrochemical methods for carrier type identification of ZnO films grown by pulsed laser deposition on InP.

Improvement in the performance of low temperature H2-O2 fuel cell with chitosanephosphotungstic acid composite membranes

Abstract Free-standing chitosan/phosphotungstic acid polyelectrolyte membranes, prepared by ionotropic gelation on alumina porous supports, were employed as proton conductor in low temperature H 2 –O 2 fuel cell. A drying step on glass substrate was introduced in the fabrication procedure to reduce shrinkage and consequent corrugation. Membranes were tested with electrodes prepared according to different procedures and with two different Pt loadings, namely 0.5 and 1 mg cm −2 . Both the investigated kinds of electrodes allowed to get very promising power peaks of 550 mW cm −2 in spite of the different Pt content. The polarization curves and the electrochemical impedance spectra suggest that…

A semiempirical correlation between the optical band gap of hydroxides and the electronegativity of their constituents

In analogy with previous results on anhydrous oxides, a correlation is proposed between the optical band gap of hydroxides and the electronegativities of their constituents. Based on the experimental results on passive hydrated layers on metals obtained in our laboratory and the literature data, it is found that the hydroxide band gap varies with the square of the difference between the electronegativities of the metallic cation and the hydroxyl group. Like in the case of anhydrous oxides, two different interpolation lines have been found forsp-metal andd-metal hydroxides, respectively. The proposed correlations predict semiconducting or insulating behavior even for the most electronegative…

Preparation and characterization of Porous Anodic Alumina Membranes as templates for the growth of metals and semiconductors nanostructures

UN PROCEDIMENTO PER IL TRATTAMENTO DI ACCIAIO ZINCATO

La zincatura viene comunemente effettuata su acciaio al carbonio per impartigli una protezione attiva, ossia una protezione catodica per anodo sacrificale, oltre che una protezione fisica di tipo barriera. La zincatura potrebbe essere utilizzata anche per barre di armature nel calcestruzzo armato nei casi in cui strutture debbano essere fabbricate in ambienti particolarmente aggressivi, quali atmosfere marine e/o industriali, dove il composito calcestruzzo/metallo può subire carbonatazione e/o attacco da cloruri. Tuttavia, la zincatura ha un effetto collaterale, ossia diminuisce l’aderenza delle barre causando problemi alla struttura. Questa controindicazione ne ha limitato l’uso in questo …

Photoelectrochemical Evidence of Cu2O/TiO2 Nanotubes Hetero-Junctions formation and their Physicochemical Characterization

Cu2O/TiO2 nanotubes heterojunctions were fabricated by electrochemical deposition of cuprous oxide on TiO2 nanotubes arrays grown by anodizing. X-ray diffraction and Raman Spectroscopy analysis allows for identification of Cu2O, whose morphological features were studied by Scanning Electron Microscopy as a function of the charge circulated during the electrodeposition step. Photoelectrochemical measurements in aqueous solutions evidenced a red shift of the light absorption threshold of TiO2 nanotubes due to the presence of cuprous oxide even for very low circulated charges, while electrochemical impedance measurements proved a significant reduction of the electrode impedance due the presenc…

Photoelectrochemical characterization of amorphous anodic films on Ti-6at.%Si

Abstract The solid state properties of anodic films grown galvanostatically on sputtering-deposited Ti–6at.%Si alloys were studied as a function of the formation voltage (5–40 V). From the photocurrent spectra a band gap of ∼3.4 eV was estimated for all the investigated thicknesses, which is almost coincident with the value measured for amorphous TiO 2 . The photocharacteristics allowed to estimate the flat band potential of the films, which resulted to be more anodic for thicker layers and allowed to evidence a change from n-type semiconducting material to insulator by increasing the formation voltage. A dielectric constant of ∼31 was estimated by differential capacitance measurements. The…

The influence of composition on the solid state properties of anodic films on Al-Ta alloys

Microelectronics is very important for almost all kinds of technology evolutions in the past four decades. In this area, the dielectrics science occupies a prominent place in providing the dominant technology in integrated capacitors or gate insulators.

Photoelectrochemical monitoring of rouging and de-rouging on AISI 316L

Electrochemical conditions for inducing rouging on surface of AISI 316L in quasi neutral aqueous solution are studied. Potentiostatic polarization at 0.6 V vs. SSC at pH ∼ 7 allowed growth of colourless passive films with a band gap slightly lower than that estimated for the oxide grown on the SS surface by air exposure due to chromium dissolution. Under stronger anodic polarization (UE = 1.5 V vs. SSC) coloured passive films are formed, mainly constituted by iron oxide according to their band gap (Eg = 2.0 eV). Etching in citric acid at 60 °C results to be effective in removing rouging.

The Influence of Composition in Determining the Solid State Properties of Al Mixed Oxides

Electrochemical Oxidation of Hf-Nb Alloys as a Valuable Route to Prepare Mixed Oxides of Tailored Dielectric Properties

Metal oxides with high dielectric constant are extensively studied in the frame of substituting SiO2 as gate dielectric in nanoelectronic devices. Here, high-k mixed HfO2/Nb2O5 oxides are prepared by a facile electrochemical route starting from sputtering-deposited Hf–Nb alloys with several compositions. Transmission electron microscopy, grazing incidence X-ray diffraction, and glow discharge optical emission spectroscopy are employed to study the oxide structures, disclosing a crystalline–amorphous transition of the electrochemically prepared oxides by increasing the Nb content. Photo-electrochemical measurements allow the observation of optical transitions ascribed to localized states ins…

A Chemical Approach to the Modelling of Band Gap of Passive Films for Corrosion Studies

Photocurrent Spectroscopy (PCS) has gained a large consideration in the last decades as in situ technique for the characterization of semiconductors and photoconducting passive film/electrolyte junctions being able to provide information on the location of characteristic energy levels like: flat band potential (Ufb), internal photoemission threshold (Eth) and band gap value (Eg)

Characterization and properties of PEO coatings on 7075 Al alloy grown in alkaline silicate electrolyte containing KMnO 4 additive

Abstract Plasma electrolytic oxidation (PEO) was used to modify the surface of 7075 Al alloy by applying a bipolar pulsed-current in a silicate based electrolyte containing 0 to 3 g L− 1 KMnO4. For the coating produced in the base electrolyte, crystalline γ-Al2O3 was the main phase, while the coatings formed at the presence of KMnO4 consisted of α-Mn2O3 containing Si and Al oxides. A pancake structure was observed on surface of the coating produced in the base electrolyte, while a foam feature along with some volcano-like areas was detected on the surface of the coatings produced in the presence of KMnO4. The KMnO4 changed the discharge type leading to diminish the pores at the metal/coatin…

Process parameters and surface treatment effects on the mechanical and corrosion resistance properties of Ti6Al4V components produced by laser powder bed fusion

Laser powder bed fusion is one of the additive manufacturing technologies which has developed more rapidly in recent years as it enables the production of very complex geometries. Titanium alloys are among the most popular materials in the aerospace industry thanks to excellent mechanical and corrosion resistance. The corrosion behavior and mechanical properties of samples made of Ti6Al4V and characterized by the geometrical features typical of brackets were investigated taking into account the effects of process parameters on porosity and microstructure. A comparison between the corrosion resistance of samples with complex geometry (3D) and specimens characterized by simple geometry (FLAT)…

Mott-Schottky analysis of differential capacitance data of passive-film electrolyte junctions. Is it really providing correct physical insights on the electronic properties of passive films and corrosion layers?

Effect of Pulse Current Mode on Microstructure, Composition and Corrosion Performance of the Coatings Produced by Plasma Electrolytic Oxidation on AZ31 Mg Alloy

Plasma electrolytic oxidation (PEO) coatings were grown on AZ31 Mg alloy in a silicate-based electrolyte containing KF using unipolar and bipolar (usual and soft-sparking) waveforms. The coatings were dual-layered consisting of MgO, MgF2 and Mg2SiO4 phases. Surface morphology of the coatings was a net-like (scaffold) containing a micro-pores network, micro-cracks and granules of oxide compounds. Deep pores were observed in the coating produced by unipolar and usual bipolar waveforms. The soft-sparking eliminated the deep pores and produced the lowest porosity in the coatings. It was found that the corrosion performance of the coatings evaluated using EIS in 3.5 wt. % NaCl solution is mostly…

Photoelectrochemical evidence of inhomogeneous composition at nm length scale of anodic films on valve metals alloys

Abstract Anodic films of different thickness (∼30 nm and 70 nm) were grown by anodizing sputtering-deposited Ta-19at% Al to different formation voltages. N incorporation into the anodic films was inducing by performing the anodizing process in ammonium containing solutions. Layered anodic films were prepared by a double formation procedure with a first anodizing step in ammonium biborate solution and second anodizing step in borate buffer solution, or vice versa. Glow Discharge Optical Emission Spectroscopy was employed to show the distribution of N across the oxide. Photoelectrochemical measurements evidenced a red shift of the light absorption threshold due to N incorporation. A model was…

Resistive switching behaviour in ZnO and VO 2 memristors grown by pulsed laser deposition

The resistive switching behaviour observed in microscale memristors based on laser ablated ZnO and VO 2 is reported. A comparison between the two materials is reported against an active device size. The results show that devices up to 300 × 300 μm 2 exhibit a memristive behaviour regardless of the device size, and 100 × 100 μm 2 ZnO-based memristors have the best resistance off/on ratio.

Amorphous to Crystalline Transition in Anodic Oxide on Ti and Ti-Si alloys: A Photoelectrochemical Study.

Electrochemical fabrication of amorphous TiO2/Poly-3,4 Ethylenedioxythiophene (PEDOT) hybrid structures for electronic devices.

Selective oxidation of aromatic alcohols in the presence of C3N4 photocatalysts derived from the polycondensation of melamine, cyanuric and barbituric acids

AbstractA set of C3N4 samples has been prepared by using melamine, cyanuric acid and barbituric acid as the precursors. The materials were subjected both to physical and chemical characterization and were used as photocatalysts for the selective oxidation of aromatic alcohols in water suspension under UV and visible irradiation. The photoactivity of the materials versus the partial oxidation of four substituted benzyl alcohols was investigated. The type and position of the substituents in the aromatic molecule influenced conversion and selectivity to the corresponding aldehyde. The presence of barbituric and cyanuric acids in the preparation method has changed the graphitic-C3N4 structure, …

Template electrosynthesis of La(OH)3 and Nd(OH)3 nanowires using porous anodic alumina membranes

High quality arrays of Ln(OH)3 (Ln = La, Nd) nanowires have been successfully fabricated for the first time by an electrochemical process using anodic alumina membrane templates. A physico-chemical characterisation of electrodeposited hydroxides has been carried out by different techniques (XRD, SEM and EDX). The results show that the synthesized nanostructures are crystalline, dense, continuous, well aligned, and with high aspect ratio, suggesting further development of possible applications in the lanthanide family species. Keywords: Nanowires, Anodic alumina membranes, Hydroxide electrodeposition, Template, Lanthanide compounds

Influence of post formation proceses on electrochemical and photoelectrochemical behaviour of TiO2 nanotubes

Corrosion and wear resistance of coatings produced on AZ31 Mg alloy by plasma electrolytic oxidation in silicate-based K2TiF6 containing solution: Effect of waveform

Abstract In this research, plasma electrolytic oxidation coatings were prepared on AZ31 Mg alloy in a silicate-based solution containing K2TiF6 using bipolar and soft sparking waveforms with 10, 20, and 30% cathodic duty cycles. The coatings displayed a net-like surface morphology consisted of irregular micro-pores, micro-cracks, fused oxide particles, and a sintered structure. Due to the incorporation of TiO2 colloidal particles and the cathodic pulse repair effect, most of the micro-pores were sealed. Long-term corrosion performance of the coatings was investigated using electrochemical impedance spectroscopy during immersion in 3.5 wt.% NaCl solution up to 14 days. The coating grown by t…

Effect of NaClO disinfection/cleaning on passive films on AISI 316L

Abstract 316 L stainless steel samples were passivated in NaClO containing solutions in order to simulate disinfection processes. Passive films were grown at the open circuit potential by immersion in NaClO aqueous solutions at different concentrations and temperature in order to understand how exposure to aggressive environments could affect subsequent corrosion resistance of SSs. In the attempt to study the passive film growth mechanism, in-situ Open Circuit Potential measurements were performed in the same growth solutions. Photoelectrochemical and impedance investigation of passive films was carried out in order to link their solid state properties with their corrosion behaviour.

Template-assisted electrodeposition of cerium oxy-hydroxide nanostructures in aqueous and organic electrolytes

Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

Cd(OH)2 nanowires (NWs) were successfully prepared by room temperature electrogeneration of base using Cd(NO3)2 aqueous electrolyte and Anodic Alumina Membrane (AAM) as template. Cd(OH)2 films have been also deposited on tin-doped indium oxide (ITO) for comparison. SEM analysis shows high quality deposits made of closely packed nanowires (NWs) into AAM and uniform flake-like surface on ITO. XRD analysis reveals that Cd(OH)2 films on ITO are polycrystalline, while the nanowires grow along the preferential directions [100] and [110]. Photoelectrochemical measurements show that Cd(OH)2 NWs are photoactive materials with indirect and direct band gap of 2.15 and 2.75 eV, respectively. Keywords: …

Growth and Characterization of Anodic Films on Al-Nb Alloys

Physico -chemical Characterization of Conversion Layers on Magnesium

The influence of surface treatment on the anodizing of magnesium in alkaline solution

Abstract The mechanism of magnesium anodizing after mechanical polishing or HF pickling was studied. X-ray Photoelectron Spectroscopy and Photocurrent Spectroscopy were employed to characterize both the initial films formed on Mg soon after surface treatments and the anodic films grown in strongly alkaline solutions. Electrochemical and capacitance measurements were performed in order to study the oxidation process and to check if the kinetic of growth fits the Mott–Cabrera high field model. From Tafel plots it was possible to estimate the activation distance, while the simulation of the barrier layer growth as a function of the potential at high scan rate allowed to estimate the other kine…

Electrochemical fabrication of Cu2O/TiO2 nanotubes junctions with visible light photoactivity

Effects of pulse current mode on plasma electrolytic oxidation of 7075 Al in Na2WO4 containing solution: From unipolar to soft-sparking regime

Abstract Plasma electrolytic oxidation coatings were produced on 7075 Al alloy in a silicate based solution containing sodium tungstate using unipolar, usual bipolar and soft-sparking bipolar pulsed current regimes. X-ray diffraction proved that the coatings contain gamma alumina and metallic tungsten. EDS results showed that the tungsten content decreases with increasing the negative half cycle. Scanning electron microscopy showed that the pancake and volcano-like were dominant morphologies for the coatings produced by the unipolar and bipolar current regimes, respectively. Under unipolar current regime, a band of large pores is observed at the metal/coating interface, while they became di…

Flamed pyrolysis titanium oxide as functional coating for Al substrate

A Chemical Approach to the Estimate of the Optical Band Gap and Bowing Parameter in Mixed d,d-Metal Oxides

Photoelectrochemical Polymerization of 3-4 Ethylene dioxythiophene on Anodic Niobium- Tantalum Mixed Oxides.

Anodization and anodic oxides

Anodizing is a low-temperature, low-cost electrochemical process allowing for the growth, on the surface of valve metals and valve metal alloys, of anodic oxides of tunable composition and properties. This article is an overview on theoretical aspects concerning the general aspects of the kinetics of growth of barrier and porous anodic oxides and some of their present and possibly future technological applications of anodic oxides. The first part of the article is devoted to anodic oxide growth models, from Guntherschulze and Betz work (in 1934) to the more recent results on barrier and porous oxide films. The second part is focused on industrial processes to fabricate anodic oxides and the…

Characterization of the Solid State Properties of Anodic Oxides Grown on Sputter-deposited Al-Nb Alloys.

Semiempirical correlation between the optical band gap of oxides and hydroxides and the electronegativity of their constituents

AbstractOn the basis of new experimental results a previous proposed correlation between the optical band gap of oxides and the difference of electronegativity of their constituents is extended to mixed crystalline and amorphous TiO2-Fe2O3 (d,d-metal oxides) as well as to amorphous passive films grown on Al-Ta, Al-Ti, Al-Nb and Al-W alloys (sp,d-metal oxides). Moreover in analogy with previous results on anhydrous oxides, a correlation is proposed between the optical band gap of hydroxides and the electronegativities of their constituents after substituting the electronegativity of hydroxilic group to that of the oxygen. Like in the case of anhydrous oxides, two different interpolation line…

From ceria nanotubes to nanowires through electrogeneration of base

The preparation of Ce(OH)3/CeO2 nanostructures (NSs) through electrogeneration of base into anodic alumina membranes was studied. The effects of solvent (alcohol and/or water), Ce3? partner anion nature (chloride or nitrate) and concentration, applied potential or current density in driving the morphology toward nanowires (NWs) and/or nanotubes (NTs) was described. The structural analysis performed by X-Ray Diffraction and Raman Spectroscopy allowed to evidence that the presence of Ce(IV) into the nanostructures strongly depends on the oxygen content in the growing environment.

Dynamic response of thin-film semiconductors to AC voltage perturbations

A theoretical treatment of a Schottky barrier dynamic response is developed on the basis of a general model of a semiconductor with thickness comparable in length to the space charge region width. It is shown that, when the space charge region approaches the metal/semiconductor interface, the electric field at this interface, induced by the charge accumulated on the metal, becomes significant with respect to the electric field induced by the charge accumulated on the semiconductor. Under this condition, the total capacitance of the Schottky barrier becomes independent of the polarization potential and tends to the value ε/L, like in a pure dielectric insulator. The term thin film is intende…

Physico-chemical Characterisation of Polypyrrole Film Grown in Aqueous and Non-aqueous Solution on Different Substrates

Electrodeposition of supported gadolinium-doped ceria solid solution nanowires

Gadolinium-ceria solid solution nanowires with tunable composition have been prepared through template cathodic electrodeposition from solutions containing Ce 3+Gd 3+ in a variable ratio. The employed template is Porous Anodic Alumina because it can function as thermal resistant separator supporting the nanowires if used as ionic conductor in Solid Oxide Fuel Cell (SOFC). Scanning Electron Microscopy of the deposited nanostructures revealed that the use of ethanol as solvent and metal chloride as electrolyte allowed to prepare continuous, compact and well defined nanowires with morphological features stable even after thermal treatment. EDX compositional analysis confirms the presence of bo…

Characterization of Anodic Oxides on Magnetron Sputtered Ta-Nb Alloys by Photocurrent Spectroscopy and Differential Admittance Measurements

Photoelectrochemical and XPS Characterization of Passive films Grown on 316L Stainless Steel in High Temperature Water

One of the major materials challenge for continued safe, reliable and cost-effective utilization of watercooled nuclear reactors for electricity production is development of improved understanding of the synergistic fundamental mechanisms responsible for corrosion and stress corrosion cracking degradation of austenitic steels and nickel base alloys

Anodic Electro Deposition of CeO2 and Co-Doped CeO2 Thin Films

CeO2 and Co containing CeO2 thin films were deposited on indium tin oxide and stainless steel by anodic electrodeposition. Scanning electron microscopy showed that the films are flat and show globular morphology and cracks resulting from volume shrinking. According to XRD and Raman Spectroscopy pure ceria layers are crystalline, while the presence of Co induces the formation of amorphous films. The good adhesion and the compactness allowed the photoelectrochemical characterization of the films. A band gap value of 2.9 eV was estimated for CeO2, while slightly higher values (̃3.0 eV) were estimated for Co containing films. A mechanism for ceria anodic electrodeposition is proposed and discus…

Photoelectrochemical evidence of nitrogen incorporation during anodizing sputtering--deposited Al-Ta alloys.

Anodic films were grown to 20 V on sputtering-deposited Al–Ta alloys in ammonium biborate and borate buffer solutions. According to glow discharge optical emission spectroscopy, anodizing in ammonium containing solution leads to the formation of N containing anodic layers. Impedance measurements did not evidence significant differences between the dielectric properties of the anodic films as a function of the anodizing electrolyte. Photoelectrochemical investigation allowed evidencing that N incorporation induces a red-shift in the light absorption threshold of the films due to the formation of allowed localized states inside their mobility gap. The estimated Fowler threshold for the intern…

A Generalized Semiempirical Approach to the Modeling of the Optical Band Gap of Ternary Al-(Ga, Nb, Ta, W) Oxides Containing Different Alumina Polymorphs

A generalization of the modeling equation of optical band gap values for ternary oxides, as a function of cationic ratio composition, is carried out based on the semiempirical correlation between the differences in the electronegativity of oxygen and the average cationic electronegativity proposed some years ago. In this work, a novel approach is suggested to account for the differences in the band gap values of the different polymorphs of binary oxides as well as for ternary oxides existing in different crystalline structures. A preliminary test on the validity of the proposed modeling equations has been carried out by using the numerous experimental data pertaining to alumina and gallia p…

Chitosan-heteropolyacid complex as high performance membranes for low temperature H2-O2 fuel cell

Behavior of alloying elements during anodizing of Mg-Cu and Mg-W alloys in a fluoride/glycerol electrolyte

Anodizing of sputtering-deposited magnesium and Mg-0.75at.%Cu and Mg-1.23at.%W alloys has been carried out in a fluoride/ glycerol electrolyte. The aims of the study were to investigate the enrichment of alloying elements in the alloy immediately beneath the anodic film and the migration of alloying element species in the film. The specimens were examined by electron microscopy and ion beam analysis. An enrichment of copper is revealed in the Mg-Cu alloy that increases with the anodizing time up to ∼6×1015 Cu atoms cm-2. Copper species are then incorporated into the anodic film and migrate outwards. In contrast, no enrichment of tungsten occurs in the Mg-W alloy, and tungsten species are im…

Electrodeposition and characterization of 1-D cerium based nanostructures

Resistive switching in microscale anodic titanium dioxide-based memristors

Licence CC BY-NC-ND The potentiality of anodic TiO2 as an oxide material for the realization of resistive switching memory cells has been explored in this paper. Cu/anodic-TiO2/Ti memristors of different sizes, ranging from 1 × 1 μm2 to 10 × 10 μm2 have been fabricated and characterized. The oxide films were grown by anodizing Ti films, using three different process conditions. Measured IV curves have shown similar asymmetric bipolar hysteresis behaviors in all the tested devices, with a gradual switching from the high resistance state to the low resistance state and vice versa, and a R_OFF/R_ON ratio of 80 for the thickest oxide film devices.

The Effect of Electrolytic Solution Composition on the Structure, Corrosion, and Wear Resistance of PEO Coatings on AZ31 Magnesium Alloy

Plasma electrolytic oxidation coatings were prepared in aluminate, phosphate, and silicate-based electrolytic solutions using a soft-sparking regime in a multi-frequency stepped process to compare the structure, corrosion, and wear characteristics of the obtained coatings on AZ31 magnesium alloy. The XRD results indicated that all coatings consist of MgO and MgF2, while specific products such as Mg2SiO4, MgSiO3, Mg2P2O7, and MgAl2O4 were also present in specimens based on the selected solution. Surface morphology of the obtained coatings was strongly affected by the electrolyte composition. Aluminate-containing coating showed volcano-like, nodular particles and craters distributed over the …

A semiempirical approach to the estimate of optical band gap in group-III nitrides alloys

Tuning of Solid-sate Properties of Al Mixed Oxides Grown on Sputter-deposited Al Alloys.

Growth and Characterization of Anodic Films on Scandium

The anodic behavior of Sc in a slightly alkaline aqueous solution is studied. Electrochemical and capacitance measurements suggest that passive films can be formed on the scandium surface under a high electric field. The formation of these layers occurs at low faradaic efficiency due to oxygen evolution. Photoelectrochemical experiments suggest the formation of a barrier layer with a thickness high enough to hinder external electron photoemission processes and allow the estimation of the bandgap of the films as a function of their formation voltage. The estimated bandgap values were lower than that reported for Sc2O3, suggesting the formation of hydrated phases and/or of a strongly oxygen d…

Study of the influence of dithizone as an eco-friendly corrosion inhibitor on the corrosion behaviour of AA7075 aluminium alloy in neutral chloride solution

The effect of 1,5-diphenylthiocarbazone (dithizone) as an eco-friendly corrosion inhibitor for protection of AA7075 aluminium alloy in chloride containing aggressive environment was studied by means of weight-loss, electrochemical measurements and Raman spectroscopy. The results indicate that the addition of dithizone decreases significantly the corrosion rate of AA7075 alloy, with efficiency proportional to the inhibitor concentration. The polarization curves show that dithizone works as mixed-type inhibitor to slow down the anodic and cathodic reaction kinetic. The morphology revealed by scanning electron microscopy and the Raman spectroscopy analysis clearly shows that the inhibitor cont…

Amorphous semiconducting passive film-electrolyte junctions revisited. The influence of a non homogeneous density of state on the differential admittance behaviour of anodic a-Nb2O5

Abstract An analysis of the electronic properties of amorphous semiconductor-electrolyte junction is reported for passive films grown on Nb in alkaline solution and in a large range of thickness (~20nm ÷ ~250nm). A modelling of electronic density of state (DOS) has been carried out by fitting EIS spectra, at different potentials and in a range of frequencies (0.1 Hz ≤ f ≤100 kHz), and differential admittance (DA) data of a-Nb 2 O 5 /El interface. The fitting of EIS and DA curves was performed by using the theory of amorphous semiconductor Schottky barrier and a non-homogeneous DOS distribution.

A critical analysis of the theory of amorphous semiconductor Schottky barrier for oxides

The Amorphous Semiconductor Schottky Barrier Approach to Study the Electronic Properties of Anodic Films on Ti

A detailed study of the electronic properties of thin (>20 nm) anodic TiO2 potentiostatically grown on titanium in two different solutions is presented. The results show that the nature of the anodizing solution affects the electronic properties of the anodic film and, more specifically, the density of electronic states (DOS) distribution. Different DOS were derived from the experimental data analyzed according to the theory of amorphous semiconductor (a-SC) Schottky barrier. It is shown that the usual non-linear and frequency dependent Mott-Schottky plots are in agreement with expected theoretical behavior of a-SC Schottky barrier.

Photoelectrochemical characterization of photocatalysts

Abstract This chapter aims to provide an overview of the photoelectrochemical characterization of semiconducting photocatalysts and, in particular, present Photocurrent Spectroscopy (PCS) as a useful tool in determining the band structure of semiconducting/insulating materials. Some fundamentals on PCS will be provided looking at the experimental setup and underlying its advantages and disadvantages. Then, the photoelectrochemical behavior of a semiconductor/electrolyte junction under irradiation will be presented, also taking into account its crystalline or amorphous nature, highlighting how it is possible to get information on the energetics of the junction. This will be exploited to show…

Effects of anodizing surface treatment on the mechanical strength of aluminum alloy 5083 to fibre reinforced composites adhesive joints

Abstract In this study, the anodizing process based on the use of tartaric sulfuric acid solution (TSA) was carried out on metal substrate to evaluate for the first time its effect on the adhesion strength and corrosion resistance of aluminium alloy (i.e., AA5083) to fibre (i.e., basalt or glass) reinforced composite adhesive joints for nautical applications. Furthermore, some TSA anodized samples were soaked in a NaOH solution to investigate the influence of this post-immersion step on the joint performances. With the aim to improve the fibre-matrix adhesion in the composite substrate thus further increasing the overall mechanical response of the joint, glass and basalt fibres were treated…

Heteropolyacids - Chitosan Membranes for H2/O2 Low Temperature Fuel Cells

Proton exchange membrane fuel cells (PEMFCs) have received much attention in recent years because of their high power density, efficiency and zero-environmental pollution. As one of the key components in fuel cells, the proton exchange membrane is expected to have high proton conductivity and good electrochemical stability. In the attempt to promote PEMCFs commercialization, high cost of fuel cell systems and short lifecycle are the two main issues that need to be addressed, thus large research effort has been devoted in developing new polymer electrolytes that can replace the usually employed proton conductors, e.g. Nafion®, with other membranes of comparable performances but lower cost. A…

A Critical Analysis on the Use of Mott-Schottky Plots to Characterise the Passive Film/Electrolyte Junction

Spettroscopia di fotocorrente e ammettenza differenziale per lo studio delle proprietà elettroniche e di stato solido di film passivi e ossidi anodici di interesse tecnologico.

Electrochemical Fabrication of High K Niobium-Tantalum Mixed Oxides/Poly 3-4 Ethylene Dioxythiophene Junctions.

Comments on 'formation and characterization of nanotubes of La(OH) 3 obtained using porous alumina membranes'

New experimental evidence concerning the formation of La(OH)3 nanowires on anodic alumina membranes by cathodic polarization in 0.05 M lanthanum nitrate solution is provided to further support the conclusions previously reached in our work (Bocchetta et al 2007 Electrochem. Commun. 9 683-8) and recently criticized by González-Rovira et al (Nanotechnology 2008 19 495305). Some unconvincing aspects of the paper of González-Rovira et al, according to which the same electrochemical process should lead to the formation of hydroxycarbonate nanotubes, are also discussed.

The multi-effects of K2TiF6 additive on the properties of PEO coatings on AZ31 Mg alloy

Abstract Plasma electrolytic oxidation of AZ31 Mg alloy was performed in an alkaline silicate-based solution containing various concentrations of K2TiF6 using unipolar waveform at a constant voltage. The surface morphology of all coatings was rough and contained a micro-pore network, micro-cracks, and granules of oxide compounds in different diameters and micro-pore levels. The coating is composed of MgO, MgF2, Mg2SiO4, SiO2 (amorphous), and TiO2 (crystalline and amorphous) phases. The average thickness of the coatings was increased by adding the K2TiF6, where EDS results showed that a skinny fluoride-rich passive layer forms. With increasing time and reaching the final potential, the TiO2 …

Characterization of Initial Films and Passivating Layers Grown on Magnesium Metal in Alkaline Solution

Photoelectrochemical Synthesis of Polypyrrole on Anodic Ta[sub 2]O[sub 5] Films

Polypyrrole film was photoelectrochemically grown on insulating Ta 2 O 5 anodic film in acetonitrile solution. A characterization by photocurrent spectroscopy (PCS) of metal/oxide/polypyrrole interface was carried out. The PCS results suggest that a metallic-like PPy is formed under illumination at constant anodic potential. By polarizing the polypyrrole at cathodic potentials a photocurrent spectrum typical of p-type semiconducting film was recorded. A scanning electron microscopy study of PPy surfaces solution side and oxide side allowed us to obtain information on the morphology of the polymer as well as a rough estimate of the film thickness and of the diameter of PPy globules at the tw…

Electrochemical Fabrication and Physicochemical Characterization of Metal/High-k Insulating Oxide/Polymer/Electrolyte Junctions

Photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered Ti-6 atom % Si alloys. Scanning electron microscopy allowed us to evidence formation of compact and uniform polymer layers on the oxide surface. Photoelectrochemical and impedance measurements showed that photopolymerization allows one to grow PEDOT in its conducting state, while a strong cathodic polarization is necessary to bring the polymer in its p-type semiconducting state. Information on the optical and electrical properties of metal/oxide/polymer/electrolyte junctions proves that PEDOT has promising performance as an electrolyte…

Valence change ReRAMs (VCM) - Experiments and modelling: General discussion

Valence change ReRAMs (VCM) - Experiments and modelling: General discussion

Electrosynthesis of Ce–Co Mixed Oxide Nanotubes with High Aspect Ratio and Tunable Composition

Cerium oxide and cobalt oxides have attracted the interest of several researchers due to their potential application in several technological fields electrochromism, lithium batteries, catalysis, etc.. Ceria has been used as a promoter in the so-called “three-way catalyst” for the control of toxic emission from automobile exhaust. The promotion consists of the enhancement of the noble metal dispersion, as well as stabilization of the supporting medium toward thermal sintering. 1,2 A direct catalytic effect of CeO2 in chemical processes such as water–gas shift reaction or NOx decomposition has been also evidenced. 3,4

Multiscale Approach in Studying the Influence of Annealing Conditions on Conductivity of TiO2 Nanotubes

Titanium oxide nanotubes (NTs) have attracted much attention during last decade due to their special characteristics such as one-dimensional highly ordered geometry with large surface area and good chemical and optical stability.

Forming-Free and Self-Rectifying Resistive Switching Effect in Anodic Titanium Dioxide-Based Memristors

The paper presents the resistive switching of electroforming-free Ti/anodic- TiO 2 /Cu memristors. Anodic TiO 2 thin films were prepared by anodizing Ti layers. Microscale devices were fabricated by direct laser-assisted photolithography. Experimental results showed a bipolar and self-rectifying behavior of the devices, which could be useful for crossbar array configurations. Moreover, a gradual resistive switching of the devices in both directions was observed, indicating the presence of multi-level resistance states.

One-step electrodeposition of superhydrophobic coating on 316L stainless steel

Superhydrophobic coatings were fabricated through a one-step electrochemical process onto the surface of 316L stainless steel samples. The presence of hierarchical structures at micro/nanoscale and manganese stearate into the coatings gave superhydrophobicity to the coating, with contact angle of ~160°, and self-cleaning ability. Corrosion resistance of 316L samples was also assessed also after the electrodeposition process through Electrochemical Impedance Spectra recorded in an aqueous solution mimicking seawater condition.

Influences of Structure and Composition on the Photoelectrochemical Behaviour of Anodic Films on Zr and Zr-20at.%Ti

Abstract A photoelectrochemical investigation on anodic films of different thickness grown on sputter-deposited Zr and Zr–20 at.%Ti was carried out. The estimated optical band gap and flat band potential of thick ( U F  ≥ 50 V) anodic films were related to their crystalline structure and compared with those obtained for thinner ( U F  ≤ 8 V/SCE) anodic oxides having undetermined crystalline structure. The E g values obtained by photocurrent spectroscopy were also compared with the experimental band gap estimated by other optical ex situ techniques and with the available theoretical estimates of the zirconia electronic structures in an attempt to reconcile the wide range of band gap data rep…

Boosting DMFC power output by adding sulfuric acid as a supporting electrolyte: Effect on cell performance equipped with platinum and platinum group metal-free cathodes

Direct methanol fuel cells (DMFCs) are promising electrochemical systems capable of producing electricity from the electrochemical oxidation of methanol and the reduction of oxygen. In this work, the effectiveness of the addition of sulfuric acid as a supporting electrolyte for methanol fuel composition was assessed. The results showed that the peak of power curve in DMFCs with Pt/C cathode electrocatalysts increased progressively from 70 mW cm−2 (0 mM of H2SO4) to 115 mW cm−2 with a concentration of 100 mM of H2SO4. These results underlined the positive effect of the addition of a supporting electrolyte in the methanol aqueous solution on the electrochemical output that was enhanced. Plati…

Photoelectrochemical and EPR features of polymeric C 3 N 4 and O-modified C 3 N 4 employed for selective photocatalytic oxidation of alcohols to aldehydes

Four different C 3 N 4 specimens have been prepared, a bulk one (MCN), a thermally etched (MCN-TE), a solid prepared by hydrothermally treating MCN with H 2 O 2 (MCN-H 2 O 2 ) and a polymeric carbon nitride-hydrogen peroxide adduct (MCN-TE-H 2 O 2 ). The principal aim of this work was to correlate the capability of the prepared material to generate reactive oxygen species (ROS), under irradiation, with their photocatalytic activities in terms of conversion and selectivity for partial oxidation reactions. Photoelectrochemical studies revealed that MCN-TE represented the best material in terms of photoconductivity, whereas MCN-H 2 O 2 was defective and evidenced a poor mobility of carriers. E…

Modeling of differential admittance behaviour of thin amorphous semiconducting film

The understanding of the electronic properties of thin oxide film is an important step toward the understanding of the mechanisms of film dissolution and breakdown as well as for their application in the field of electrolytic capacitors and solar energy conversion. From this point of view the correct location of the characteristic energy levels (flat band potential, Ufb, and conduction (valence) band edge EC (EV)), of a passive film/electrolyte junction is the preliminary task for a deeper understanding of the mechanism of charge transfer at oxide/electrolyte interface. At this aim the most frequently employed method to locate such characteristic energy levels of semiconductor oxide/electro…

Characterization of Thin Passive Film-Electrolyte Junctions.The Amorphous Semiconductor (a-SC) Schottky Barrier Approach

The knowledge of the solid-state properties of passive film is a preliminary task for a full understanding of the electron and ion transfer processes at the metal/oxide and oxide/electrolyte interface. Both processes are of paramount importance in determining the mechanism of film growth and dissolution as well as in determining the nature of the breakdown during the growth of anodic oxide films or the onset of generalized or localized corrosion process (1-2). With very few exceptions, it is a common belief, that most of anodic oxide films, grown on metals and alloys in aqueous solutions, display a semiconducting or insulating behaviour. It is also very well known that in many cases the ini…

Effect of Composition on the Photoelectrochemical Behaviour of Anodic Oxides grown on Aluminium Alloys

Electroplated bismuth absorbers for planar NTD-Ge sensor arrays applied to hard x-ray detection in astrophysics

Single sensors or small arrays of manually assembled neutron transmutation doped germanium (NTD-Ge) based microcalorimeters have been widely used as high energy-resolution detectors from infrared to hard X-rays. Several planar technological processes were developed in the last years aimed at the fabrication of NTD-Ge arrays, specifically designed to produce soft X-ray detectors. One of these processes consists in the fabrication of the absorbers. In order to absorb efficiently hard X-ray photons, the absorber has to be properly designed and a suitable material has to be employed. Bismuth offers interesting properties in terms of absorbing capability, of low heat capacity (needed to obtain h…

Tuning of the Mg Alloy AZ31 Anodizing Process for Biodegradable Implants

Coatings were grown on the AZ31 Mg alloy by a hard anodizing process in the hot glycerol phosphate-containing electrolyte. Anodizing conditions were optimized, maximizing corrosion resistance estimated by impedance measurements carried out in Hank's solution at 37 °C. A post anodizing annealing treatment (350 °C for 24 h) allowed us to further enhance the corrosion resistance of the coatings mainly containing magnesium phosphate according to energy-dispersive X-ray spectroscopy and Raman analyses. Gravimetric measurements revealed a hydrogen evolution rate within the limits acceptable for application of AZ31 in biomedical devices. In vitro tests demonstrated that the coatings are biocompati…

Photoelectrochemical evidence of inhomogeneous composition at nm length scale of anodic films on valve metals alloys

Anodic films of different thickness (∼30 nm and 70 nm) were grown by anodizing sputtering-deposited Ta-19at% Al to different formation voltages. N incorporation into the anodic films was inducing by performing the anodizing process in ammonium containing solutions. Layered anodic films were prepared by a double formation procedure with a first anodizing step in ammonium biborate solution and second anodizing step in borate buffer solution, or vice versa. Glow Discharge Optical Emission Spectroscopy was employed to show the distribution of N across the oxide. Photoelectrochemical measurements evidenced a red shift of the light absorption threshold due to N incorporation. A model was proposed…

Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

Abstract Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H 2 –O 2 fuel cell allowing to get peak power densities up to 350 mW cm −2 . Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm −1 .

Cerium oxyhydroxide nanowire growth via electrogeneration of base in nonaqueous electrolytes

The preparation of compact cerium oxyhydroxide nanowires into anodic alumina membranes from cerium chloride in ethanol solution via electrogeneration of base is reported. Scanning electron microscopy analyses indicate that dense, well-aligned, and highly ordered nanowires can be formed in a wide range of applied potentials and current densities in alcoholic solution. The employment of water brings to a hybrid nanotube/nanowire structure, suggesting a key role of the electrolyte nature in determining the morphology of the deposit. Electrochemical findings and X-ray diffraction analysis have shown that nanowires are constituted by a Ce(III)/Ce(IV) oxyhydroxide that can be completely oxidized …

Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: general discussion

Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: General discussion

Physicochemical characterization of passive films on niobium by admittance and electrochemical impedance spectroscopy studies

An analysis of the electronic properties of amorphous semiconductor-electrolyte junction is reported for thin (D ox < 20 nm) passive film grown on Nb in acidic electrolyte. It will be shown that the theory of amorphous semiconductor-electrolyte junction (a-SC/EI) both in the low band-bending and high band-bending regime is able to explain the admittance data of a-Nb 2 O 5 /El interface in a large range (10 Hz-10 kHz) of frequency and electrode potential values. A modelling of experimental EIS data at different potentials and in the frequency range of 0.1 Hz-100 kHz is presented based on the theory of amorphous semiconductor and compared with the results of the fitting of the admittance data…

Tuning of solid state properties of Al-Ta mixed oxides

METODO PER IL TRATTAMENTO SUPERFICIALE DI LEGHE DI MAGNESIO PER APPLICAZIONI BIOMEDICALI

L’invenzione oggetto di questo brevetto riguarda il processo di anodizzazione per la produzione di rivestimenti (coatings) su leghe di Magnesio AZ31. Queste leghe sono potenzialmente utilizzabili per la produzione di dispositivi biomedicali quali protesi e stent che sono soggetti a fenomeni di corrosione all’interno del corpo umano che ne possono compromettere il funzionamento. Il vantaggio di queste leghe sta nel fatto che possiedono ottime proprietà meccaniche (il modulo elastico delle leghe di Magnesio AZ31 risulta essere confrontabile con quello dell’osso umano) e risultano biodegradabili, ovvero svolgono la loro funzione di sostegno meccanico per lo stretto periodo necessario, e quindi…

Tailoring of the solid state properties of Al-Nb mixed oxides: A photoelectrochemical study

Al-Nb containing mixed oxides were grown by anodizing sputter-deposited Al-Nb alloys of different compositions. A photoelectrochemical investigation was carried out in order to estimate the band gap, flat band potential, and conductivity type of these oxides as a function of their composition. The dependence of the band gap on the composition of mixed sp-d metal oxides has been rationalized by using a semiempirical correlation between the difference of electronegativity and band gap of oxides proposed in the literature some years ago and recently tested for regular d-d metal mixed oxides. The band gap increase observed as a function of Al content into the oxides seems mainly depending on th…

Photoelectrochemical Polymerization of 3-4 Ethylenedioxythiophene on High k Niobium-Tantalum Mixed Oxides.

Physico-chemical Properties of Anodic Oxide Films: from Passivity to Electronics

Anodized Ti-Si Alloy as Gate Oxide of Electrochemically-Fabricated Organic Field-Effect Transistors

Organic field-effect transistors were fabricated using an electrochemical route. The dielectric oxide was grown by anodization of a Ti:Si alloy, while 3,4-polyethylenedioxythiophene has been employed as a semiconducting polymer. OutputI-Vcharacteristics showed a transistor effect dependent on dielectric thickness. Fitting between I-V measurements and theoretical simulations in the triode region confirmed the presence of a conduction path through the polymer which degrades the electrical characteristics of the devices.

Tailoring of the Solid State Properties of Al–Nb Mixed Oxides: A Photoelectrochemical Study

Al–Nb containing mixed oxides were grown by anodizing sputter-deposited Al–Nb alloys of different compositions. A photoelectrochemical investigation was carried out in order to estimate the band gap, flat band potential, and conductivity type of these oxides as a function of their composition. The dependence of the band gap on the composition of mixed sp–d metal oxides has been rationalized by using a semiempirical correlation between the difference of electronegativity and band gap of oxides proposed in the literature some years ago and recently tested for regular d–d metal mixed oxides. The band gap increase observed as a function of Al content into the oxides seems mainly depending on th…

Heterogeneous crystallization of zinc hydroxystannate on galvanized steel for enhancing the bond strength at the rebar/concrete interface

Abstract Zinc hydroxystannate (ZnSn(OH)6) coatings were deposited on galvanized carbon steel samples by an electroless heterogeneous crystallization process. Structural and morphological features of the coatings as a function of the immersion time were determined by X-ray diffraction, Raman Spectroscopy and Scanning Electron Microscopy revealing the presence of truncated octahedrons of crystalline ZnSn(OH)6. Electrochemical characterization in a simulated concrete pore solution without and with addition of chloride ions proved that the cathodic protection is preserved and that ZnSn(OH)6 improved the corrosion resistance of the rebars. Pull-out tests demonstrated an enhanced bond strength at…

Corrosion resistance of passive films on different stainless steel grades in food and beverage industry

Abstract Passive films were grown on 304 L, 316 L and Duplex stainless steels by immersion at open circuit potential in solutions mimicking food and beverage industry environments. In acidic food stainless steel surfaces are covered by Cr rich passive films, and generalized dissolution occurs on their surface with consequent ions release into the electrolyte. In fatty food the concentration of released ions is significantly lower since generalized corrosion does not occur, but the loss on MnS inclusions strongly reduces the polarization resistance in this environment especially for 304 L due to its higher localized corrosion susceptibility with respect to the other grades.

Physicochemical Characterization of anodic film on Titanium prepared by Pedeferri’s Treatment.

One-step electrochemical synthesis and physico-chemical characterization of CdSe nanotubes

Abstract Stoichiometric CdSe nanotubes (NTs) with a length of ∼700 nm have been successfully grown by one-step electrochemical technique into anodic alumina membranes. Cyclovoltammetric method has been performed using porous anodic alumina as template electrode and an electrochemical bath containing Cd 2+ ions and SeO 2 . The as-prepared NTs have been identified as face-centred-cubic CdSe by XRD, while micro-Raman analysis reveals the typical peaks of nanostructured CdSe. The stoichiometric deposition of CdSe NTs formation is suggested by EDX analysis, with an average atomic percentage of Cd:Se of ∼0.93. Photoelectrochemical measurements reveal that CdSe NTs are photoactive materials with d…

Assessment on the use of the amorphous semiconductor theory for the analysis of oxide films

Abstract Although the theory of Schottky barrier in amorphous semiconductors is generally accepted, the limits of validity of such theory have not yet been explored. The classic semi-analytical solution is obtained under the constraint of constant electronic density of states (DOS) distribution in the mobility gap. In order to take into account the presence of a DOS variable in energy, a semi-empirical corrective power law was introduced in this paper. It is shown that the equations derived for thick films maintain their validity also in the case of thin films, provided that the space charge region width remains lower than 70% of the whole film thickness. A new expression based on the use o…

Electrochemical Tantalum Oxide for Resistive Switching Memories

Redox-based resistive switching memories (ReRAMs) are strongest candidates for the next-generation nonvolatile memories fulfilling the criteria for fast, energy efficient, and scalable green IT. These types of devices can also be used for selector elements, alternative logic circuits and computing, and memristive and neuromorphic operations. ReRAMs are composed of metal/solid electrolyte/metal junctions in which the solid electrolyte is typically a metal oxide or multilayer oxides structures. Here, this study offers an effective and cheap electrochemical approach to fabricate Ta/Ta2O5-based devices by anodizing. This method allows to grow high-quality and dense oxide thin films onto a metal…

Formation and photo-electrochemical characterization of anodic films on different valve-metal alloys

Hybrid organic-inorganic membranes for low temperature H2-O2 fuel cell

The influence of electrolyte composition on the solid state properties of anodic films on Ta-Nb alloys

Characterization of Passive Film/Electrolyte Junctions by Photocurrent Spectroscopy and Impedance Measurements

Recent advances in photocurrent spectroscopy of passive films

Abstract The quantitative application of photocurrent spectroscopy (PCS) for the in-situ determination of the composition of passive films and corrosion layers is reviewed in the light of recent theoretical advances, that have allowed to relate the measured optical gaps to the Pauling electronegativities of the film components. The correlations derived are tested versus recent experimental results regarding mixed oxides, anhydrous passive films on metallic alloys and hydroxide layers. The effect of the eventual long-range disorder into the passive film on the optical band gap values is also discussed. New experimental evidence reported for mixed d,d-metal oxides and passive films on sp,d-me…

Effect of Incorporation of Foreign Species on the Solid State Properties of Anodic Films on Ti

Photoelectrochemical Synthesis of Conducting Polymers on Large Band Gap Nb2O5 and Ta2O5 Anodic Oxide Films

Physico-chemical Characterization of Aluminium Oxide Films Grown on Etched Foils for Electrolytic Capacitors

Photoelectrochemical Synthesis of Conducting Polymers Layers on Large Band Gap Nb2O5 and Ta2O5 Anodic Oxides Films

Formation of anodic films on sputtering-deposited Al–Hf alloys

Abstract The growth of barrier-type anodic films at high efficiency on a range of sputtering-deposited Al–Hf alloys, containing from 1 to 95 at.% Hf, has been investigated in ammonium pentaborate electrolyte. The alloys encompassed nanocrystalline and amorphous structures, the latter being produced for alloys containing from 26 to 61 at.% Hf. Except at the highest hafnium content, the films were amorphous and contained units of HfO 2 and Al 2 O 3 distributed relatively uniformly through the film thickness. Boron species were confined to outer regions of the films. The boron distributions suggest that the cation transport number decreases progressively with increasing hafnium concentration i…

Photocurrent Spectroscopy Applied to the Characterization of Passive Films on Sputter-Deposited Ti-Zr Alloys

Abstract A photoelectrochemical investigation on thin (⩽13 nm) mixed oxides grown on sputter-deposited Ti–Zr alloys of different composition by air exposure and by anodizing (formation voltage, UF = 4 V/SCE) was carried out. The experimental results showed that the optical band gap, E g opt , increases with increasing Zr content in both air formed and anodic films. Such behaviour is in agreement with the theoretical expectation based on the correlation between the band gap values of oxides and the difference of electronegativity of their constituents. The flat band potential of the mixed oxides was found to be almost independent on the Ti/Zr ratio into the film and more anodic with respect …

Dielectric Properties of Al-Nb Amorphous Mixed Oxides

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Photoelectrochemical evidence of Nitrogen Incorporation during Anodizing of Sputtering-Deposited Al-Ta alloys

Anodic films were grown to 20 V on sputtering-deposited Al–Ta alloys in ammonium biborate and borate buffer solutions. According to glow discharge optical emission spectroscopy, anodizing in ammonium containing solution leads to the formation of N containing anodic layers. Impedance measurements did not evidence significant differences between the dielectric properties of the anodic films as a function of the anodizing electrolyte. Photoelectrochemical investigation allowed evidencing that N incorporation induces a red-shift in the light absorption threshold of the films due to the formation of allowed localized states inside their mobility gap. The estimated Fowler threshold for the intern…

An Electrochemical Investigation on the Adhesion of As-Formed Anodic TiO2 Nanotubes Grown in Organic Solvents

Electrodeposition of CeO2 and Co-Doped CeO2 Nanotubes by Cyclic Anodization in Porous Alumina Membranes

An anodic electrodeposition process is proposed to prepare CeO2 and Co-doped CeO2 nanotubes. Anodic alumina membrane is used as template and linear sweep voltammetry is employed to allow the formation of nanotubes without alumina dissolution. SEM micrographs showed large arrays of well defined and aligned NTs, which resulted to be crystalline soon after deposition according to XRD diffraction patterns and Raman Spectroscopy.

Synthesis and characterization of zinc hydroxystannate films

Growth and field crystallization of anodic films on Ta–Nb alloys

The growth behavior of amorphous anodic films on Ta–Nb solid solution alloys has been investigated over a wide composition range at a constant current density of 50 Am−2 in 0.1 mol dm−3 ammonium pentaborate electrolyte. The anodic films consist of two layers, comprising a thin outer Nb2O5 layer and an inner layer consisting of units of Ta2O5 and Nb2O5. The outer Nb2O5 layer is formed as a consequence of the faster outward migration of Nb5+ ions, compared with Ta5+ ions, during film growth under the high electric field. Their relative migration rates are independent of the alloy composition. The formation ratio, density, and capacitance of the films show a linear relation to the alloy compos…

Effect of Molybdate on Corrosion Performance of Oxide Coating Produced on 7075 Al Alloy Using PEO

In this research, plasma electrolytic oxidation (PEO) coatings were prepared on 7075 Al alloy in a silicate-based solution with Na2MoO4 additive using a unipolar waveform at constant current density. The coatings displayed micro-pores, micro-cracks, pancake-like and crater-like features, and also solidified molten oxide particles on the surface. The coatings were majorly composed of Al2O3 (&gamma;, &delta;, and &alpha;), SiO2 (amorphous), and MoO3 phases, which confirms the incorporation of molybdenum in the case of additive-containing coatings. Molybdenum species were transported through cracks, channels, and micropores, as the ready access pathways into the coating and partly sealed the c…

Physicochemical Characterization of Passive Films and Corrosion Layers by Differential Admittance and Photocurrent Spectroscopy

Two different electrochemical techniques, differential admittance and photocurrent spectroscopy, for the characterization of electronic and solid state properties of passive films and corrosion layers are described and critically evaluated. In order to get information on the electronic properties of passive film and corrosion layers as well as the necessary information to locate the characteristic energy levels of the passive film/electrolyte junction like: flat band potential (Ufb), conduction band edge (EC) or valence band edge (EV), a wide use of Mott-Schottky plots is usually reported in corrosion science and passivity studies. It has been shown, in several papers, that the use of simpl…

Characterization of Anodic Oxides on Titanium by Photocurrent and Differential Admittance Techniques

Photo-Electrochemical deposition of Poly-3,4 Ethylenedioxythiophene on Anodic Films on Ti-Si Alloys.

Pulsed laser deposition of ZnO and VO2 films for memristor fabrication

Memristors are resistive switching memory devices which have attracted much attention over the last years for high-density memory applications because of their simple structure, small cell size, high speed, low power consumption, potential for 3-D stacking and excellent compatibility with the complementary metal-oxide-semiconductor (CMOS) technology [1]. Beside nonvolatile memory applications, memristors have been also proposed for other different applications including biosensors [2] and neuromorphic [3] circuits. The device structure is simply an oxide material sandwiched between two metal electrodes. The switching behavior is not only dependent on the oxide material but also on the choic…

Silicate and Hydroxide Concentration Influencing the Properties of Composite Al2O3-TiO2 PEO Coatings on AA7075 Alloy

This work evaluates the effect of sodium meta-silicate pentahydrate (SMS) and potassium hydroxide concentrations on properties of Al2O3-TiO2 coatings produced through plasma electrolytic oxidation in a solution containing 3 g L−1 potassium titanyl oxalate, (PTO), using a unipolar waveform with constant current density. The surface and cross-section characteristics of PEO coatings including morphology, elemental distribution, and phase composition were evaluated using FESEM, EDS, and XRD techniques. Voltage-time response indicated the concentration of SMS and KOH had a significant effect on the duration of each stage of the PEO process. More cracks and pores were formed at the higher concent…

Anodic Alumina Membranes for Fuel Cell Technology and Nanostructure Template-assisted Deposition

Anodic alumina membranes (AAMs) with ordered porous structure have been investigated as possible ionic conducting membranes for thin film (= 50μm) fuel cells (TFFC) and as templates for the production of a variety of nanostructure arrays. The aims of this work are to present some of our recent results pertaining to the functionalisation of AAM with proton conductors for the production of membranes to be used in hydrogen/oxygen TFFC, at low or intermediate temperature (25°C ≦ T ≦ 250°C), and to the fabrication by template technique of nanowires/nanotubes arrays of oxide and hydroxides for possible future technological application.

From CeO2 Nanotubes to Nanowires through Electrogeneration of Base

Abstract not Available.

Growth and characterization of anodic films on Sc in aqueous solutions

Band gap narrowing and dielectric constant enhancement of (NbxTa(1-x))2O5 by electrochemical nitrogen doping

Abstract Anodic films were grown to 5 V and 50 V on Nb, Ta and Ta-Nb sputtering deposited alloys in 0.1 M ammonium biborate solutions in order to induce N incorporation. Their properties were compared to those of N free anodic films grown to the same formation voltages in 0.1 M NaOH. Photoelectrochemical measurements evidenced the presence of optical transitions at energy lower than the band gap of the oxides, attributed to localized states located close to the valence band mobility edge of the films, generated by N 2p orbitals, with consequent narrowing of the band gap. Since N incorporation occurs in the outer 70% of the anodic films, the dependence of the measured photocurrent as a funct…

Influence of synthesis conditions on the performance of chitosan–Heteropolyacid complexes as membranes for low temperature H2–O2 fuel cell

Flat, free-standing chitosan/phosphotungstic acid (PTA) polyelectrolyte membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by H3PW12O40. Scanning electron microscopy revealed the formation of compact and homogeneous membranes, whose thickness resulted to be dependent on chitosan concentration and reticulation time. X-ray diffraction and Fourier transform infrared spectroscopy (FTIR) evidenced the formation of almost amorphous membrane without appreciable concentration of not protonated NH2 groups and PTA3- ions with preserved Keggin structure. Membranes were tested as proton conductor in low temperature H2-O2 fuel…

Structural and Photocurrent Characterization of Anodic Oxides on Titanium

Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

Recent advances on physico-chemical characterization of passive films by EIS and differential admittance techniques

Abstract Thin Nb2O5 anodic films (∼20 nm thick) grown in phosphoric acid solution have been characterised by EIS and differential admittance study in a large range of potential and frequency. The overall electrical behaviour has been interpreted by means of the theory of amorphous semiconductor Schottky barrier in presence of a non-constant density of states (DOS). A comparison of DOS for films grown in different electrolytes is reported.

Double Step Electrochemical Process for the Deposition of Superhydrophobic Coatings for Enhanced Corrosion Resistance

Superhydrophobic surface on anodized AA5083 sample was obtained by an electrochemical process. Scanning Electron Microscopy and Fourier Transform Infrared Spectroscopy analyses revealed the hierarchical structure of the coating and the presence of manganese stearate. These features were crucial for the coating superhydrophobicity, demonstrated by a measured contact angle of ~ 163° and its self-cleaning ability. Electrochemical characterization in an aqueous solution mimicking seawater proved an enhanced corrosion resistance due to the superhydrophobic coating with respect to anodized AA5083 sample that also lasted after 20 immersion days in Cl- containing electrolyte.

Characterization of the Solid State Properties of Anodic Oxides on Ta-Nb Alloys as a Function of the Anodizing Conditions

Tantalum oxide, niobium oxide and Ta-Nb containing mixed oxides were grown by anodizing sputter-deposited TaxNb(1-x) alloys with 0 ≤ x ≤ 1. A photoelectrochemical investigation was performed in order to estimate the band gap values of the oxides as a function of their composition as well as to estimate their flat band potential. Differential capacitance curves were recorded for all the investigated oxides in a wide range of electrode potential and for several frequencies of the alternative signal. The dependence of C on the applied potential and a.c. frequency was interpreted on the basis of amorphous semiconductor Schottky barrier, and allowed to estimate the dielectric constant of the inv…

Anodic Alumina Membranes for Fuel Cell Technology and Nanostructure Template -assisted Deposition

Formation and photo-electrochemical characterization of anodic films on valve-metal alloys

The formation of anodic films on valve metals alloys has been studied as a function of alloy composition and anodizing conditions. Photocurrent Spectroscopy technique (PCS) has been used to determine the band gap (E g) and the flat band potential (Vfb,) of oxides grown on these alloys. The formation of insulating-like or semiconducting oxide films has been evidenced as a function of initial alloys composition. The composition of "mixed oxide" has been related to the measured optical band gap values on the basis of experimental results and previous proposed correlation.

Influence of Anodic and Thermal Barrier Layers on Physicochemical Behavior of Anodic TiO2 Nanotubes

Electrochemical and photo-electrochemical behavior of self-organized TiO2 nanotubes formed in organic solvents have been studied by taking into account the formation of new barrier layers beneath nanotubes either due to the anodic polarization in aqueous solutions or air exposure during high temperature annealing. It has been shown that before annealing, electrochemical and photoelectrochemical answers are dominantly controlled by the physicochemical properties of the anodic barrier layer. Annealing in air at sufficiently high temperatures changes the initial amorphous structure of as-prepared nanotubes and forms a new oxide layer below them due to thermal oxidation of underneath titanium. …

The influence of nitrogen incorporation on the optical properties of anodic Ta2O5

Abstract Anodic oxides were grown on sputter-deposited Ta in different aqueous solutions. A photoelectrochemical investigation was performed in order to estimate the band gap of the films as a function of the anodizing bath composition and formation voltage, i.e. thickness. Photoelectrochemical results provided evidence of sub-band gap photocurrent for films formed in a bath containing ammonium ions at pH 9. Elemental depth profiles obtained by glow discharge optical emission spectroscopy revealed the presence of nitrogen species in the outer part of the anodic films, which is bonded to Ta according to XPS analysis. A mechanism of nitrogen incorporation is proposed in order to account for t…

Effect of TiO2 and Al2O3 Addition on the Performance of Chitosan/Phosphotungstic Composite Membranes for Direct Methanol Fuel Cells

Composite chitosan/phosphotungstic acid (CS/PTA) with the addition of TiO2 and Al2O3 particles were synthesized to be used as proton exchange membranes in direct methanol fuel cells (DMFCs). The influence of fillers was assessed through X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, liquid uptake, ion exchange capacity and methanol permeability measurements. The addition of TiO2 particles into proton exchange membranes led to an increase in crystallinity and a decrease in liquid uptake and methanol permeability with respect to pristine CS/PTA membranes, whilst the effect of the introduction of Al2O3 particles on the characteristics of membranes is almost the op…

Effects of Pulse Current Mode on Plasma Electrolytic Oxidation of 7075 Al in KMnO4Containing Solution

Plasma electrolytic oxidation of 7075 Al alloy was performed in alkaline silicate electrolyte containing KMnO4as an additive using unipolar (U) and bipolar pulsed current modes (B1 and B2). The coating grown using the bipolar current with longer cathodic pulse time (B2) revealed a more dense foam-like surface morphology with fewer volcano areas providing higher thickness, which is mainly raised by reduction in discharge intensity. Also, a lower concentration of electrolyte elements (Si and Mn) was incorporated into the coating providing a brighter appearance. EIS results showed very high inner layer resistances for the coatings indicating this layer controls the overall corrosion performanc…

Characterization of Thin Passive Film-Electrolyte Junctions. The Amorphous Semiconductor (a-SC) Schottky Barrier Approach.

A detailed study of the electronic properties of thin (< 20 nm) anodic TiO2 potentiostatically grown on titanium in two different solutions is presented. The results show that the nature of the anodizing solution affects the electronic properties of the anodic film and in particular the density of electronic state (DOS) distribution. Different DOS were derived from the experimental data analyzed according to the theory of amorphous semiconductor (a-SC) Schottky barrier. It is shown that the usual non-linear and frequency dependent Mott-Schottky plots are in agreement with expected theoretical behaviour of a-SC Schottky barrier. It is shown the importance of the DOS distribution in determini…

The effect of hydration layers on the anodic growth and on the dielectric properties of Al2O3 for electrolytic capacitors

Hydrous films were grown on high purity and cubicity Al foils for electrolytic capacitors in deionized water, ethylene glycol - deionized water and in glycerol - deionized water for different immersion times. According to the X-ray diffraction patterns the hydration treatment allowed to grow a pseudo boehmite layer on Al surface whose morphology is appreciably affected by the bath composition. Capacitance measurements and photoelectrochemical findings suggest that a more compact barrier layer forms during the immersion in alcohol containing solutions. The hydration in water allowed to save energy and to prepare more blocking oxide films. The beneficial effect of hydration in hot water on th…

Optimization of anodizing process of tantalum for Ta2O5-based capacitors

Anodic oxides were grown to 50 V on Ta in several organic ions containing anodizing baths. Their properties were compared with anodic Ta oxide film grown to the same formation voltage in 0.1 M NaOH. Anodizing process carried out in sodium citrate led to the growth of the anodic oxide with the best blocking properties whilst, when Ta is anodized in sodium adipate, a significant part of the circulated charge is wasted in side reactions, such as oxygen evolution. Photoelectrochemical measurements showed the presence of optical transitions at energy lower than the band gap for the anodic films grown in citrate and tartrate electrolytes, attributed to localized electronic states located close to…

Influence of film thickness and amorphous nature on the differential capacitance measurements of a-Nb2O5/electrolyte junction

Photocurrent spectroscopy study of passive films on hafnium and hafnium–tungsten sputtered alloys

Abstract Anodic and air-formed films on sputtered Hf and W–Hf alloys of different composition have been investigated by Rutherford back scattering, photocurrent spectroscopy (PCS) and transmission electron microscopy (TEM) techniques. In alkaline solutions the PCS data suggest the formation on Hf metal of a duplex layer with anodic hafnia covered by an external layer of composition close to HfO(OH) 2 . This last compound is also present on Hf air-formed films. In acidic solutions the initial oxy-hydroxide film disappears at high anodising potentials ( V f >10 V). In the case of W–Hf alloys films of different composition and semiconducting behaviour are formed by air exposure or by anodising…

Development of an Electrochemical Balance to Measure Quantitatively Hydrogen Generation during Electrochemical Processes

A new method to measure the amount of hydrogen generated from the surface of an immersed electrode is presented in this work. The method consists of a mechanical balance with a horizontal arm attached to two hydrogen-collecting containers that are submerged in two independent electrochemical cells. One of the two cells (the test cell) contains the electrode of interest, generating an unknown amount of hydrogen, whereas the other cell (the measurement cell) contains an inert electrode that is used to evolve an amount of hydrogen equal to that generated in the test cell, such as the mechanical equilibrium between the sides of the balance is constantly maintained. Adequate electrical connectio…