Bubble behaviour during oxygen and hydrogen evolution at transparent electrodes in KOH solution

For oxygen and hydrogen evolving transparent nickel electrodes in KOH solutions, parameters characterizing the behaviour of bubbles which are adhered to the electrode surface during gas evolution, have been determined in dependence on current density, i, velocity of solution flow, v, pressure, p, temperature, T, and concentration of KOH. Based on experimental data a new basic bubble parameter, J, has been introduced, which accounts for the bubble behaviour. It has been found that J = a₁i^h₁ and J/(J₀?J) = a₂v^h₂ where J₀ = J at v = 0 ms^?1 and a₁,a₂h₁ and h₂ are empirical constants; some of these depend on nature of gas evolved. Moreover, the parameter J is almost proportional to the KOH concentration, increases in a decreasing rate with increasing pressure and increases linearly with the reciprocal of the absolute temperature.     

Electrochemical impedance spectroscopy on porous electrodes

Electrochemical d.c. and a.c. measurements have been carried out on porous Raney nickel in H₂-saturated 0.1 M, 1 M, and 6 M NaOH solutions atT=303 K and 333 K using rotating-disc and static-plaar electrodes. For comparison, measurements were also performed on graphite-cloth and graphite-felt electrodes. From polarization curves and current transients obtained in the potential range of the hydrogen evolution and hydrogen oxidation reactions the dependence of the electrocatalytic activity of Raney nickel on the prepolarization conditions was studied. Impedance spectra in the frequency range 1 mHzf 10 kHz were used to determine the characteristic pore parameters and to identify the kinetic behaviour of the porous electrodes by application of transfer function analysis using non-linear fit routines.     

Electrochemical preparation of amorphous Fe-P alloys

Optimum conditions have been established for the electrodeposition of amorphous fe-P alloys from sulphate electrolytes, containing complex-forming additives (glycine and oxalic acid) and sodium hypophosphite. It was shown that the increase of pH, current density and glycine content in the plating solution leads to a decrease of the amount of phosphorus in the Fe-P alloy. The cathodic current yield decreases with the increase of glycine concentration in the electrolyte. Small amounts of Cu²⁺ and Mn²⁺ act as brighteners. Sodium hypophosphite exerts a depolarizing effect on the alloy formation process. This effect is more pronounced at low hypophosphite concentrations and low cathodic current densities (CCD). The measurement of the cathodic potential during the deposition of the investigated alloy provides no evidence for a concentration change of phosphorus in the electrodeposited layers. No qualitative alterations of the surface morphology of the amorphous coatings studied have been established as the composition of the alloy and the plating conditions are changed.     

Electrochemical impedance spectroscopy of fully hydrated Nafion membranes at high and low hydrogen partial pressures

The proton transport mechanism in fully hydrated Nafion 117 membranes was examined via electrochemical impedance spectroscopy (EIS) and steady-state current–potential measurements both in a symmetric H₂, Pt|Nafion|Pt, H₂ cell and in a H₂, Pt|Nafion|Pt, air PEM fuel cell with hydrogen partial pressure values, PH₂, varied between 0.5 kPa and 100 kPa. In agreement with recent studies it is found that for low PH₂ values the steady-state current–potential curves exhibit bistability and regions of positive slope. In these regions the Nyquist plots are found to exhibit negative real part impedance with a large imaginary component, while the Bode plots show a pronounced negative phase shift. These observations are consistent with the mechanism involving two parallel routes of proton conduction in fully hydrated Nafion membranes, one due to proton migration in the aqueous phase, the other due to proton transfer, probably involving tunneling, between adjacent sulfonate groups in narrow pores. The former mechanism dominates at high PH₂ values and the latter dominates in the low PH₂ region where the real part of the impedance is negative.     

Electrolytic oxygen evolution on Ni-Co-P alloys

Electrolytically obtained Ni–Co–P alloys exhibit amorphous structure. On heating these alloys to 773 K crystalline nickel and cobalt phosphide phases, and also nickel crystallites, are formed. After cathode-anode polarization of the amorphous and crystalline Ni–Co–P alloys in 5m KOH for 18 h, oxygen-cobalt compounds together with crystalline or amorphous nickel phosphides appear on the electrode surface. The evolution of oxygen from 5m KOH was studied on Ni–Co–P alloys prepared in this way. The Tafel parameters were determined and it was ascertained that the values of directional coefficients of the Tafel lines are comparable with those obtained for spinel NiCo₂O₄ oxides, while calculated values of the exchange currents for the oxygen evolution reaction are dependent on the chemical composition of the alloy. The rate of electrolytic oxygen evolution is virtually identical for amorphous and crystalline Ni–Co–P alloys of the same chemical composition. The highest rate of oxygen evolution was found for the alloy containing 15–20% Ni, 66–73% Co and 12–14% P.     

Electrochemical and chemical reactions in baths for plating amorphous alloys

Deposition of amorphous alloys of (W, Co, B) is accompanied by anodic decomposition of ammonium citrate (pH 8.5) electrolyte. Products of decomposition include amines and nitro-organic compounds. Also some nitrite, and probably nitrate, is found in solutions electrolyzed for a long time. The anodic decomposition processes are catalyzed by cobalt.     

Electrochemical impedance spectroscopy study on silver coated metallic implants

This work presents the preparation of nano-structured silver coatings on TiAl₆V₄ and CoCrMo alloys by a pulse current technique and the study of time dependent electrochemical behaviour of silver coated metallic implants. EIS data as a function of immersion time in 0.9 wt% NaCl solution have been obtained to clarify the electrochemical processes occurring in the system. During early stage immersion (1–2 days), the impedance response shows near capacitive behaviour. As the time passes, the electrolyte gradually penetrates the silver coating and the sandblasted metallic implants. The silver comes into contact with the electrolyte and the conditions for galvanic corrosion are fulfilled. Due to the potential difference between silver coating and the metallic alloy, discrete anodic and cathodic areas are formed, which result in the release of silver, since the silver acts as an anode in galvanic cells. The cathode process is the reduction of the dissolved oxygen at the surface of the substrate. For antimicrobial applications of nanosilver coated TiAl₆V₄ and CoCrMo alloys, it is very important to maintain the continuous release silver ions. Degradation of silver coatings have been traced and confirmed by different methods such as SEM micrographs, EDX analysis, EIS measurements and solution analysis by ICP-MS methods.     

Electrochemical studies of self-assembled monolayers using impedance spectroscopy

Self-assembled monolayers (SAMs) using various organic molecules were constructed on thin thermal silicon dioxide on silicon structures. These structures have potential bio-applications. The monolayers are part of a capacitor sensor based on the electrolyte-insulator-silicon (EIS) structure. The main goal of this work is to investigate the ability of SAMs for acting as an intermediate layer between aqueous solutions and silicon based biosensors. This work presents monolayers based on trimethoxy silanes with various functional groups such as: (a) (3-aminopropyl)-trimethoxysilane, (b) octadecyltrimethoxysilane and (c) trimethoxy(3,3,3-trifluoropropyl)silane. The biosensor is a differential sensor with a built in reference based on the structure of electrolyte-insulator-silicon or in ion-sensitive-field-effect-transistors (ISFETs). While the methyl and fluorine groups can act as the reference part, which is passive to the bio-molecules detection, the capacitor containing the amine groups has the sensing capabilities to the biological molecules. The amine (NH₂) tail groups can be active for those attachments via glutaraldehyde.The film's study and characterization was made by spectroscopic ellipsometry, contact angle method (CA) and FT-IR spectroscopy. The electrical methods such as capacitance-voltage (C-V) and electrochemical impedance spectroscopy (IS) were used to investigate the whole electrolyte/SAM/SiO₂/Si structure. We will show the detection capabilities of these 2D structures, its electrical equivalent model through a simulation fitting and will discuss the application of those structures to bio-sensitive metal/oxide/silicon (MOS) devices.     

Electrochemical impedance spectroscopy inspection of composite adhesive joints

Lap shear joints comprised of aluminum-aluminum, aluminum-glass fiber-reinforced polymer (GFRP), aluminum-carbon fiber-reinforced polymer (CFRP), CFRP-CFRP, CFRP-GFRP and GFRP-GFRP, were exposed to 95% relative humidity (RH) at 50°C, 70°C and 90°C, to salt fog and to a 90°C/95%RH freeze cycle. Electrochemical impedance spectroscopy (EIS) spectra were taken across the whole bonded assembly using an EIS corrosion sensor. Periodically, some specimens were pulled to obtain bond strength as a function of exposure. As expected, the higher the temperature, the faster the bond degradation. The low-frequency impedance correlated with bond strength of the humidity-exposed specimens and showed the same Arrhenius dependence, suggesting that moisture absorption by the adhesive was the limiting factor in bond performance and that EIS has the potential to nondestructively track bond health and warn of deterioration.     

Electrochemical impedance spectroscopy of a free-standing oxide film

The corrosion of low carbon steel in natural sea-water is characterized by the formation and growth of compact and thick layers composed of oxides, insoluble salts and organic materials. These layers are the result of corrosion processes induced by local environmental conditions, water oxygen supply; ionic species; bacteria and organic matter. The exchange of various species (ions, molecules, gas) between sea-water and the rust layers or the metal depends both on the kinetics of the Faradaic reactions of the entities with either the oxides or the metal, as well as on their transport properties through the different strata of the rust layers. In this work, an impedance study was carried out using the 4-electrodes cell arrangement with corrosion products picked up on steel sheet piling immersed for 25 years and analyzed as free standing membranes. This new approach is a good way to reach the specific transport and transfer properties of the oxide without being blurred by the metal influence. The physical model developed in this work was based on a transmission line, and accurately described the experimental diagrams. The electronic resistivity of the oxide layer, its porosity, the mean pore size and the reaction kinetics parameters could be determined from the fittings.     

Electrochemical impedance spectroscopy of patterned steady states on electrode surfaces

In this work we report modelling of electrochemical impedance spectra for the CO bulk electrooxidation on Pt, an electrochemical system with an S-shaped current-potential curve (S-NDR (negative differential resistance) system). Galvanostatic control and parameter ranges, in which self-organized stationary CO-coverage patterns exist on the electrode surface are considered. The patterns consist of two stationary domains with different CO coverages. The simulations show that at very low frequencies the applied current modulation imposes a domain size modulation which occurs at nearly constant electrode potential. Consequently, the interface impedance modulus tends to zero at very low frequencies and no negative real impedance can be observed in the simulated impedance spectra. For higher modulation frequencies, the faster current modulation affects the domain size expansion and contraction processes, inducing an increase of the interface impedance modulus and a dependence of its phase on the frequency. These results demonstrate that the dynamics of pattern formation affects considerably the linear response of an electrochemical system. Furthermore, they suggest that measurements of impedance spectra can offer valuable information on the dynamics of pattern formation and of the electrochemical processes involved.     

Effect of cobalt deposits on nickel substrates on the oxygen evolution reaction in KOH

Cobalt deposits taking the form of cobalt nodules were obtained on nickel substrates in a bath containing dissolved cobalt sulphate and ammonium citrate at pH 9.8 and 23°C. Oxygen discharge was investigated on those electrodes in 40 wt % KOH solution at temperatures ranging between 40 and 80°C. Up to a cobalt loading of 12 mg cm^–2, the larger the loading, the larger the electrode/solution interface, which resulted in improved electrocatalytic activity with the loading. The electrocatalytic activity was also largely temperature-dependent.     

Electrochemical and oxygen reduction behaviour of solid silver-bismuth/antimony electrodes in KOH solutions

Oxygen reduction behaviour at silver-low bismuth/antimony electrodes was investigated by electrochemical methods in KOH solutions. The electrochemical redox characteristics such as peak multiplicity, peak currents and peak potentials on these electrodes under both potentiostatic steady state and cyclic voltammetric conditions were obtained. The anomalies associated with the redox peak potential values both in the anodic and cathodic branches of the cyclic voltammograms were attributed to the distinct electrochemical behaviour of bismuth/antimony on the electrode surface along with silver. The behaviour of these electrodes for the electrocatalytic cathodic reduction of oxygen was also investigated both by potentiostatic steady state and cyclic voltammetric techniques under rotating conditions. The kinetic parameters corresponding to the electrochemical reduction of oxygen on these electrodes were obtained. These electrodes were ranked with respect to their electrocatalytic activity both for the oxygen reduction and evolution reactions.     

Electrochemical hydrogen evolution on polypyrrole from alkaline solutions

Thin films of conductive polypyrrole (PPy) were formed electrochemically from aqueous sulfuric acid. The films showed good electrocatalytic properties towards hydrogen evolution (h.e.r) from alkaline solutions on planar and packed-bed iron electrodes. Current–potential relations were measured at various temperatures and KOH concentrations on Fe, Ni and Fe/PPy planar electrodes. The current was found to be constant during 40 h of operation. SEM micrographs showed no difference in the morphology before and after this period. The activation energy for h.e.r. was found to be 50.2, 58.5 and 33.4 kJ mol^–1 for Fe, Ni and Fe/PPy planar electrodes, respectively. The results showed that Fe/PPy can be used to produce hydrogen at both ambient and relatively high temperatures 70 C. The polypyrrole coating on iron screens was found to reduce the potential required to sustain a specific rate of hydrogen generation and, hence, the energy consumed during the process.     

Electrochemical absorption-desorption of hydrogen on multicomponent Zr-Ti-V-Ni-Cr-Fe alloys in alkaline solution

Multicomponent Zr-Ti-V-Ni-Cr-Fe and Zr-Ti-V-Ni-Cr alloy electrodes, with various Ti and Zr ratios, have been studied in alkaline solution by means of potentiodynamic current-overvoltage and galvanostatic overpotential-time responses during long-term continuous and intermittent charge-discharge cycles. The pressure-composition isotherms for absorption/desorption of hydrogen, evaluated from the equilibrium potential, have been compared with the gas phase isotherms. The kinetic data demonstrate the reversibility of hydrogen electrosorption in the investigated systems. An increased discharge efficiency has been established for electrodes with lower values of both the activation and diffusion resistance. The alloy with Fe and Ti:Zr at the atomic ratio 2:1 prepared by using vanadium-ferro-alloy is shown to meet the requirements for the negative electrode in secondary nickel-metal hydride batteries.     

Electrochemical impedance spectroscopy of the alkaline manganese dioxide electrode

Two-probe electrochemical impedance spectroscopy measurements were carried out on the electrolytic manganese dioxide electrode in concentrated KOH electrolytes under a variety of experimental conditions. These included varying the electrode thickness and compaction pressure, electrolyte content and concentration, degree of manganese dioxide reduction and the presence of TiO₂ (anatase) as an additive. The overall electrode impedance was found to decrease when thin electrodes, prepared under high compaction pressures, with an excess of electrolyte, were used. The impedance of the EMD/electrolyte interface was also minimized when 5.0 M KOH was used as the electrolyte. This correlates with a maximum in electrolyte conductivity. The electrode impedance also increased as the degree of EMD reduction was increased, as was expected. Under these experimental conditions the electrode impedance increased in the presence of TiO₂ (anatase), which has negative implications for its commercial use. This conclusion was reached despite the differences in experimental conditions between this work and in commercial applications. An equivalent circuit was also derived and used as an aid in interpreting the impedance data.     

Electrochemical impedance spectroscopy study of waterborne coatings film formation

In order to establish electrochemical impedance spectroscopy (EIS) as a viable quantitative method for characterization of latex film formation, three waterborne acrylate and styrene–acrylate polymer dispersions were periodically analyzed during a course of 2 weeks. Impedance spectra were fitted on the base of equivalent circuit consisting of a capacitor in parallel with a Warburg element representing film capacitance and the extent of ion diffusion through the film. Calculated EIS parameter values showed a decrease in Warburg diffusion over time, which is a result of particle coalescence and in agreement with the established theory of latex film formation. Atomic force microscopy (AFM) of the samples showed a smoothing of the surface and blurring of interparticle boundaries which confirmed that EIS can be used to study film formation of latex.     

Electrochemical impedance spectroscopy of oxidized and hydrogen-terminated nitrogen-induced conductive ultrananocrystalline diamond

We have studied the electrochemical impedance spectroscopy of conductive ultrananocrystalline diamond (UNCD) modified by either oxidation or hydrogenation surface treatments. The impedance was measured in the frequency range from 0.1 Hz to 40 kHz at different DC voltages and the results fitted to an equivalent electrical circuit. Despite the complexity of the conductive UNCD surface, composed of sp³-bonded grains and grain boundaries with a high content of sp²-bonded carbon atoms, a Randles circuit with a constant phase element (CPE) for the capacitive element provided a reasonable model for both terminations. However, the parameters of the CPE were very different for each termination. Taking into account the results obtained, we propose that the interfacial impedance of oxidized UNCD is dominated by the oxidized sp²-bonded carbon atoms present at the grain boundaries, and the interfacial impedance of hydrogen-terminated UNCD is governed by both the grain boundaries and the grains.     

Investigation of the hydrogen evolution reaction at a 10 wt% palladium-dispersed carbon electrode using electrochemical impedance spectroscopy

The hydrogen evolution reaction (h.e.r.) at a 10 wt % palladium-dispersed carbon (Pd/C) electrode in 0.1 m NaOH solution has been investigated with reference to that on carbon (Vulcan XC-72) and palladium foil electrodes by analysing the a.c.-impedance spectra combined with cyclic voltammograms. From the coincidence of the maximum charge transfer resistances and the minimum hydrogen evolution resistances for the h.e.r. at the respective electrode potential for the Pd/C, carbon and Pd foil electrodes, it is suggested that the h.e.r. at the Pd/C electrode takes place along with the absorption and diffusion of hydrogen above –1.10 V vs SCE, whereas the former dominates over the latter below –1.10V vs SCE. In the case of the Pd foil electrode the transition of absorption and diffusion to evolution occurs at –0.96V vs SCE. In contrast to the Pd/C and Pd foil electrodes the h.e.r. occurs strongly at the carbon electrode below –1.20V vs SCE. The hydrogen evolution overpotential on the Pd/C electrode is decreased by 0.10 V in comparison to the carbon electrode due to the larger electrochemical active area of the finely dispersed Pd particles.     

Electrochemical impedance spectroscopy for in situ petroleum analysis and water-in-oil emulsion characterization

The measurement of electrochemical impedance spectroscopy used in situ is a suitable technique for the characterization of oil and water-in-oil emulsions. Nyquist diagrams for dehydrated oils are characterized by the formation of one semi-circle. The equivalent circuit proposed for the dehydrated oil is a resistance and capacitor (R_OC_O) in parallel. The resistance and conductivity of the oil calculated by impedance were 2.96 Gohm and 486 nS m^?1, respectively. Nyquist diagrams for the system composed of water emulsions in oil are mainly characterized by two semi-circles with different relaxation for oil and water-in-oil emulsions. The equivalent circuit is formed by R_O and CPE_O in parallel and in series with the arrangement of R_W/O and CPE_W/O in parallel, where R_O and CPE_O represents the oil, and R_W/O and CPE_W/O represents water-in-oil emulsions. The resistance of oil (R_O) and water-in-oil (R_W/O) emulsions increase with the increasing amount of water in the preparation. The increase in resistance shows that the emulsions become more stable with the addition of water. This result is consistent with the formation of rigid films on water–oil interfaces. The impedance measurements were applied to the analysis of the demulsification of the water-in-oil emulsions under an electrostatic field.