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…

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…

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…

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…

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

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.

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…

Redshift of absorption threshold of TiO2 Nanotubes due to Cu2O electrodeposition

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.

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 …

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…

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 …

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 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

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.

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 …

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…

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…

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…

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…

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…

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.…

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 …

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.

Resistive switching of anodic TiO2-based Memristors

In recent years, memristors have attracted great attention owing to their simple fabrication process, high scalability, good compatibility with the CMOS technology, high switching speed, low power consumption and low cost for next-generation non-volatile memory technology [1]. The basic cell structure of a memristor is an insulator sandwiched between two metal electrodes. Among the materials being studied for memristors fabrication, binary metal oxides, such as TiO2, are most favourable because of their simple constituents, compatible with CMOS processes, and resistive to thermal/chemical damages. Anodizing is a an electrochemical low cost process carried out at room temperature to grow oxi…

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 …

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.

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

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)

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)…

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…

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, …

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

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.

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

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

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…

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

Influence of post-treatment time of trivalent chromium protection coating on aluminium alloy 2024-T3 on improved corrosion resistance

Abstract Low corrosion protection performances of Trivalent Chromium Process (TCP) coatings with reference to Chromium Conversion Coatings (CCC) deposited on aluminium alloys can be overcome by application of post-treatment processes. This work shows the effect of post-treatment bath (containing hydrogen peroxide and lanthanum salt) on the chemical composition, structure and the corrosion performances of TCP coating deposited on AA 2024-T3 aluminium alloy. Different times of post-treatment bath were applied on the TCP coating and the samples were analyzed by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), X-ray Photoelectron Spectroscopy (XPS) and Glow Discharge-Optical Emission …

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…

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…

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.

ELECTROCHEMICAL FABRICATION OF METAL/OXIDE/CONDUCTING POLYMER JUNCTIONS FOR ELECTRONIC DEVICES

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.

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.

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…

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…

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.

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…

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

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

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

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…

Effect of High Temperature Oxidation Process on Corrosion Resistance of Bright Annealed Ferritic Stainless Steel

The corrosion resistance of stainless steels is determined by the thickness, structure, composition and electronic properties of the oxide layers grown on their surface and isolating the metallic substrate from the environment. In the present work, ex situ XPS (X-Ray Photoelectron Spectroscopy) and ToF-SIMS (Time of Flight Secondary Ions Mass Spectrometry) have been combined to in situ PCS (PhotoCurrent Spectroscopy) in order to perform an integrated physicochemical characterization of surface oxide films grown on bright annealed ferritic stainless steel (AISI 434) as-received and after thermal post-treatment in air. The surface oxide film on as-received samples has a bilayer structure with…

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…

Room temperature electrodeposition of photoactive Cd(OH)2 nanowires