0000000000553631
AUTHOR
Andrea Zaffora
showing 55 related works from this author
Energy harvesting by waste acid/base neutralization via bipolar membrane reverse electrodialysis
2020
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…
Enhancing Biocompatibility and Antibacterial Activity of Ti6Al4V by Entrapping Ag and Hydroxyapatite Inside Alginate Filled Pores of TiO 2 Layer Grow…
2022
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
2017
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
2018
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…
Photocurrent Spectroscopy in Corrosion and Passivity Studies. A Critical Assessment
2016
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…
Fabrication of Bismuth Absorber Arrays for NTD-Ge Hard X-ray Microcalorimeters
2020
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 …
Methanol and proton transport through chitosan-phosphotungstic acid membranes for direct methanol fuel cell
2020
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
2017
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…
The Effect of Anodizing Bath Composition on the Electronic Properties of Anodic Ta-Nb Mixed Oxides
2022
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 …
Corrosion of stainless steel in food and pharmaceutical industry
2021
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…
Electrochemically prepared oxides for resistive switching memories
2018
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…
Highly Active and Stable NiCuMo Electrocatalyst Supported on 304 Stainless Steel Porous Transport Layer for Hydrogen Evolution in Alkaline Water Elec…
2023
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…
The influence of composition on band gap and dielectric constant of anodic Al-Ta mixed oxides
2015
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…
On the modelling of an Acid/Base Flow Battery: An innovative electrical energy storage device based on pH and salinity gradients
2020
Abstract Electrical energy storage can enhance the efficiency in the use of fluctuating renewable sources, e.g. solar and wind energy. The Acid/Base Flow Battery is an innovative and sustainable process to store electrical energy in the form of pH and salinity gradients via electrodialytic reversible techniques. Two electromembrane processes are involved: Bipolar Membrane Electrodialysis during the charge phase and its opposite, Bipolar Membrane Reverse Electrodialysis, during the discharge phase. For the first time, the present work aims at predicting the performance of this energy storage device via the development of a dynamic mathematical model based on a multi-scale approach with distr…
Modellazione matematica di una Acid/Base Flow Battery: un dispositivo innovativo di accumulo di energia elettrica basato su gradienti di salinità e d…
2019
La Acid/Base Flow Battery (AB-FB) è una batteria innovativa che rappresenta un metodo sostenibile di immagazzinare energia elettrica. Questa batteria può, in linea teorica, garantire una densità di energia pari a 11 kWh/m3 che è un valore maggiore rispetto a quello fornito dalle tecnologie attualmente più utilizzate nel mondo quali quelle che sfruttano l’energia idroelettrica, l’energia osmotica o ancora l’aria compressa. La batteria AB-FB accumula energia sottoforma di gradienti di salinità e di pH. In particolare, essa funziona grazie ad una unità chiamata “stack” al cui interno ospita una serie di canali che permettono il passaggio di soluzioni elettrolitiche a diversi pH e concentrazion…
Performance of H2-fed fuel cell with chitosan/silicotungstic acid membrane as proton conductor
2020
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
2016
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…
TiO2 in memristors and resistive random access memory devices
2021
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
2018
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…
Critical Review—Photocurrent Spectroscopy in Corrosion and Passivity Studies: A Critical Assessment of the Use of Band Gap Value to Estimate the Oxid…
2017
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
2017
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…
Fabrication and characterization of micrometer-scale ZnO memristors
2015
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.…
Electrochemical Oxidation of Hf-Nb Alloys as a Valuable Route to Prepare Mixed Oxides of Tailored Dielectric Properties
2018
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…
Photoelectrochemical evidence of inhomogeneous composition at nm length scale of anodic films on valve metals alloys
2016
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…
Anodization and anodic oxides
2018
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…
Photoelectrochemical evidence of nitrogen incorporation during anodizing sputtering--deposited Al-Ta alloys.
2015
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 Polymo…
2021
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…
Resistive switching in microscale anodic titanium dioxide-based memristors
2018
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.
Photoelectrochemical characterization of photocatalysts
2021
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…
Rhodamine (B) photocatalysis under solar light on high crystalline ZnO films grown by home-made DC sputtering
2018
Abstract ZnO thin films were deposited by home-made DC sputtering of zinc target under mixed gases (Argon, Oxygen) plasma on glass substrates. Films were deposited by varying oxygen partial pressure (PO2) from 0.09 to 1.3 mbar in the deposition chamber, at a fixed substrate temperature of 100 °C. The samples were characterized by photoluminescence (PL), X-ray diffraction (XRD), optical transmissions (UV–vis), scanning electron microscopy (SEM) and electrical (Hall effect) measurements. The results indicate that by varying the oxygen pressure in the deposition chamber, the films show a precise and well defined photoluminescence emissions for each range of pressure covering almost the entire …
Valence change ReRAMs (VCM) - Experiments and modelling: General discussion
2019
Valence change ReRAMs (VCM) - Experiments and modelling: General discussion
Forming-Free and Self-Rectifying Resistive Switching Effect in Anodic Titanium Dioxide-Based Memristors
2018
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
2021
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.
Boosting DMFC power output by adding sulfuric acid as a supporting electrolyte: Effect on cell performance equipped with platinum and platinum group …
2023
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 alde…
2019
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…
Electroplated bismuth absorbers for planar NTD-Ge sensor arrays applied to hard x-ray detection in astrophysics
2018
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
2021
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…
Ionic shortcut currents via manifolds in reverse electrodialysis stacks
2020
Abstract Reverse electrodialysis (RED) is a blue energy technology for clean and sustainable electricity harvesting from the mixing entropy of salinity gradients. Recently, many efforts have been devoted to improving the performance of RED units by developing new ion-exchange membranes and by reducing the detrimental phenomena affecting the process. Among these sources of “irreversibility”, the shortcut currents (or parasitic currents) flowing through alternative pathways may affect the process efficiency. Although such phenomena occur in several electrochemical processes (e.g. fuel cells, bipolar plate cells and vanadium redox flow batteries), they have received a poor attention in RED uni…
Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: general discussion
2019
Electrochemical metallization ReRAMs (ECM) - Experiments and modelling: General discussion
METODO PER IL TRATTAMENTO SUPERFICIALE DI LEGHE DI MAGNESIO PER APPLICAZIONI BIOMEDICALI
2019
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…
Heterogeneous crystallization of zinc hydroxystannate on galvanized steel for enhancing the bond strength at the rebar/concrete interface
2021
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…
Electrochemical Tantalum Oxide for Resistive Switching Memories
2017
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…
On the modelling of an Acid/Base Flow battery: an innovative electrical energy storage device based on pH and salinity gradients
2019
The Acid/Base Flow Battery (AB-FB) is an innovative and sustainable way to store electric energy. It can theoretically guarantee an energy density of about 11 kWh/m3, which is higher than that provided by pumped hydropower, osmotic energy storage and compressed air. The AB-FB stores energy as pH and salinity gradients by employing a stack provided with (i) channels, hosting the solutions at difference pH and concentrations, separated by (ii) monopolar and bipolar ion exchange membranes. Two different membrane processes are involved: the Bipolar Membrane Electrodialysis (ED-BM) as charging step and its opposite, Bipolar Membrane Reverse Electrodialysis (RED-BM) as discharging step. The prese…
Band gap narrowing and dielectric constant enhancement of (NbxTa(1-x))2O5 by electrochemical nitrogen doping
2018
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…
Double Step Electrochemical Process for the Deposition of Superhydrophobic Coatings for Enhanced Corrosion Resistance
2021
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.
Effect of TiO2 and Al2O3 Addition on the Performance of Chitosan/Phosphotungstic Composite Membranes for Direct Methanol Fuel Cells
2023
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…
Optimization of anodizing process of tantalum for Ta2O5-based capacitors
2020
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…
Photoelectrochemical evidence of Nitrogen Incorporation during Anodizing of valve metals alloys
2015
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.
Solid State Properties of Anodic Hf-Nb Mixed Oxides
2016
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…
Photocurrent Spectroscopy in Corrosion and Passivity Studies. A Critical Assessment
2016
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
2016
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 …
Resistive switching of anodic TiO2-based Memristors
2018
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…
The influence of composition on the solid state properties of anodic films on Al-Ta alloys
2015
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 evidence of inhomogeneous composition at nm length scale of anodic films on valve metals alloys
2015
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…
Photoelectrochemical evidence of Nitrogen Incorporation during Anodizing of Sputtering-Deposited Al-Ta alloys
2016
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…