Anodic dissolution of aluminum and anodic passivation in [EMIm]Cl-based ionic liquids

The anodic dissolution of aluminum in Lewis acidic ionic liquids consisting of AlCl3 and 1-ethyl-3-methylimidazolium chloride was studied using linear sweep and cyclic voltammetry, an electrochemical quartz crystal microbalance (EQCM) and chronopotentiometry at ambient temperature. Anodic passivation of the working electrode was observed in a 2:1 electrolyte while no passivation was found in a 1.5:1 electrolyte. Chronopotentiometry proves the passivation to be caused by local solidification of the electrolyte due to an increase in the aluminum concentration near the anode. EQCM data support these results

Electrochemical Phase Formation of Ni and Ni-Fe Alloys in a Magnetic Field

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field

Electrochemical preparation of Cobalt-Samarium nanoparticles in an aprotic ionic liquid

Electrochemical preparation of Co-Sm nanoparticles was conducted in an aprotic room temperature ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing Co(TFSA)2 and Sm(TFSA)3. The cyclic voltammetry on a glassy carbon (GC) electrode indicated the electrochemically generated Sm(II) reacted with Co(II) at 25 °C. Potentiostatic cathodic reduction on a GC electrode in BMPTFSA containing 30 mM Co(TFSA)2 and 5 mM Sm(TFSA)3 at 25 °C gave the deposits, which were found to be composed of Co and Sm by energy dispersive X-ray spectroscopy (EDX). The deposits were found to be the aggregates of SmCo7 nanoparticles by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The formation of SmCo7 nanoparticles dispersed in the ionic liquid was also confirmed by TEM. SmCo7 nanoparticles were considered to form by the disproportionation reaction of Sm(II) in the presence of elementary Co, which was formed by the reduction of Co(II) by Sm(II)

Ultrasound assisted electrodeposition of Cu-SiO2 composite coatings: Effect of particle surface chemistry

Electrodeposition of Cu-SiO2 composite coatings from an alkaline non-cyanide electrolyte containing glutamate as complexing agent was studied. Silica mesoporous particles were synthesized using a modified Stöber methodology, and later their surface chemistry was changed by functionalizing them with 3-aminopropyltriethoxysilane. Particles microstructure and morphology were characterized (SEM, TEM, XRD) and their charging behavior in several electrolytes was studied through ζ-potential measurements. Galvanostatic deposition was performed in electrolytes containing both as-prepared and functionalized SiO2 at various current densities, and the influence of ultrasonic irradiation (37 Hz) was evaluated. For some experiments, 1.5 g L− of Polyquaternium 7 were added to the solution. SEM and XRD were used to characterized coatings morphology and microstructure, whereas EDS was used to estimate SiO2 wt%. The results showed that the effect of ultrasound on the codeposition process depends on current density and particle surface chemistry. All the trends observed in this study could be explained taking into account ζ-potential values recorded and previously reported theories. Adjusting the experimental conditions, it was possible to obtain deposits with SiO2 contents of ≈5 wt%. Finally, it was found that both ultrasonic irradiation and Polyquaternium 7 affect the morphology and crystal orientation of the deposits.Fil: Bengoa, Leandro Nicolás. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Ispas, Adriana. Technische Universität Ilmenau; AlemaniaFil: Bengoa, Jose Fernando. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; ArgentinaFil: Bund, A.. Technische Universität Ilmenau; AlemaniaFil: Egli, Walter Alfredo. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones en Tecnología de Pinturas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones en Tecnología de Pinturas; Argentin

Nanoparticle gas phase electrodeposition: fundamentals, fluid dynamics, and deposition kinetics

This communication uncovers missing fundamental elements and an expanded model of gas phase electrodeposition; a relatively new and in large parts unexplored process, which combines particle generation, transport zone and deposition zone in an interacting setup. The process enables selected area deposition of charged nanoparticles that are dispersed and transported by a carrier gas at atmospheric pressure conditions. Two key parameters have been identified: carrier gas flow rate and spark discharge power. Both parameters affect electrical current carried by charged species, nanoparticle mass, particle size and film morphology. In combination, these values enable to provide an estimate of the gas flow dependent Debye length. Together with Langmuir probe measurements of electric potential and field distribution, the transport can be described and understood. First, the transport of the charged species is dominated by the carrier gas flow. In close proximity, the transport is electric field driven. The transition region is not fixed and correlates with the electric potential profile, which is strongly dependent on the deposition rate. Considering the film morphology, the power of the discharge turns out to be the most relevant parameter. Low spark power combined with low gas flow leads to dendritic film growth. In contrast, higher spark power combined with higher gas flow produces compact layers

Detection of flexibly bound adsorbate using the nonlinear response of quartz crystal resonator driven at high oscillation amplitude

Flexibly bound heavy adsorbates as antibodies, biomarkers, microbeads, bacteria do not produce response at quartz resonators accounted by their mass alone, which complicates their acoustic detection. To resolve this problem, an anharmonic detection technique (ADT) has been developed. It generates higher harmonics by applying a high voltage (0.7–10 V) fundamental frequency excitation to 14.3 MHz AT-cut quartz crystal. Due to non-linearity the parameters of generated oscillations depend on the amplitude A of the applied signal, being proportional to A2 for the fundamental resonance frequency and mainly to A3 for the amplitude of generated 3rd harmonics. The coefficients of proportionality depend on number of attached particles, but not on their mass and can be calculated from the phenomenological model based on Duffing equation with damping. The model was tested in liquids of various viscosity, on composite layer including polymer film with deposited gold nanoparticles and in electrochemical mode for E.-coli adsorption

An electrochemical quartz crystal microbalance study on electrodeposition of aluminum and aluminum-manganese alloys

The electrodeposition process of aluminum and aluminum-manganese alloys was studied in situ, by using an electrochemical quartz crystal microbalance, EQCM, with damping monitoring, in AlCl3 based ionic liquids. Cyclic voltammetry, potentiostatic and galvanostatic deposition were performed at different temperatures, from 25°C up to 100°C. The morphology of the deposits was investigated by SEM and AFM, and their composition by EDX. The stoichiometry of the alloys was calculated from the EQCM data, based on Sauerbrey's equation. We could show that for thin films electrodeposited on gold electrodes, one can tune their morphology, and in the case of the alloys, also their composition, by modifying the deposition current or potential, as well as by modifying the temperature of the electrolyte. The morphology of the deposits changed gradually with increasing the amount of Mn in the electrolyte from a polyhedral like structure for Al films to round granules for the AlMn alloys. The mechanism for electrodeposition and dissolution of Al and AlMn alloys were analyzed and discussed based on the EQCM data

Electrochemical Phase Formation of Ni and Ni-Fe Alloys in a Magnetic Field

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field

Electrochemical Phase Formation of Ni and Ni-Fe Alloys in a Magnetic Field

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field