Identification of inductive behavior for polyaniline via electrochemical impedance spectroscopy

Polyaniline (PANI) film electrodeposited in HCl medium using cyclic voltammetry (CV) with an upper potential limit of 0.90 V, exhibited an inductive behavior. PANI films deposited with different conditions were subjected to various applied potentials and the impedance characteristics were recorded through electrochemical impedance spectroscopy (EIS). The impedance results clearly reveal the existence of inductive behavior to PANI. Inductive behavior was observed for PANI films deposited with conditions which favor benzoquinone/hydroquinone (BQ/HQ) formation and further evidenced by X-ray photoelectron spectroscopy (XPS). A comparative analysis of the EIS and XPS results of PANI films prepared under similar conditions with the upper potential limits of 0.75 and 0.90 V, respectively, clearly documented that the presence of BQ/HQ, the degradation product of PANI, formed during the electrochemical polymerization at the upper potential limits causes inductive behavior to PANI.     

Investigation of solid oxide fuel cell short stacks for mobile applications by electrochemical impedance spectroscopy

Solid oxide fuel cells (SOFC) for mobile applications are developed and investigated at the German Aerospace Center (DLR) in Stuttgart. Therefore a light-weight stack design was developed in cooperation with the automotive industry (BMW/Munich, Elring-Klinger/Dettingen, ThyssenKrupp/Essen) and the Research Center Jülich (FZJ). This concept is based on the application of stamped metal sheet bipolar plates, into which the SOFC cells are integrated by brazing technology. For the development and the investigation of the SOFC cells and short stacks, the electrochemical impedance spectroscopy (EIS) is an important and useful characterization method. The paper concentrates on the investigation and on the electrochemical testing of the SOFC short stacks with sintered anode-supported cells (ASC). The short stacks were electrochemically characterized mainly by electrochemical impedance spectroscopy, by current-voltage measurements and by long-term measurements. The cells and stacks were operated at different temperatures, varying fuel gas compositions, different fuel gas flow rates and at different electrical current loads. The influence of these operating conditions on the electrochemical performance of the short stacks is outlined. The nature of losses, e.g. ohmic and the polarization resistances of the electrodes were examined and determined by fitting of the impedance spectra to an equivalent circuit.     

Investigation of electrode composition of polymer fuel cells by electrochemical impedance spectroscopy

In order to optimize the electrode composition and performance of Polymer Fuel Cells and to reduce the production cost of membrane electrode assemblies (MEAs), different MEAs using different catalyst powders, carbon supported and unsupported catalysts with different proton conducting electrolyte powder (Nafion) content were produced by using a dry powder spraying technique developed at German Aerospace Research Center (DLR, Deutsches Zentrum fuer Luft- und Raumfahrt). The electrochemical characterization was performed by recording current-voltage curves and electrochemical impedance spectra (EIS) in the galvanostatic mode of operation at 500 mA cm⁻². The evaluation of the measured impedance spectra with an adequate equivalent circuit shows that the cathode of the fuel cell is very sensitive to the electrode composition whereas the contribution of the anode is very small and invariant to the electrode composition. Furthermore, it could be shown for the first time using electrolyte powder in the electrodes that the charge transfer of the cathode decreasing monotonically with increasing electrolyte content in the cathode. These findings suggest that with increasing electrolyte content in the electrodes, in particular in the cathode, the utilization degree of the catalyst increasing linearly with increasing electrolyte content in the electrode.     

Electrochemical impedance spectroscopy of lead(II) ion-selective solid-state membranes

Silver sulphide/lead sulphide membranes were studied using electrochemical impedance spectroscopy. The influence of the electrolyte concentration and the membrane thickness were evaluated. The complex impedance plots have shown two capacitive loops: one at high frequency range, related with the charge transfer resistance at the interface membrane-Ag and a second one at low frequency range, associated with the diffusion process through the membrane. A simple model was used to take into account the experimental results: the changes of the potential with the time and the electrolyte concentration; the changes of the charge transfer resistance and the diffusion resistance with the electrolyte concentration. An empirical equation was used to calculate the diffusion coefficient of Ag⁺ inside the membrane.     

Stainless steel electrode characterizations by electrochemical impedance spectroscopy for dye-sensitized solar cells

Electrochemical impedance spectroscopy (EIS) was used to understand the electrochemical mechanisms which appear in dye-sensitized solar cells (DSSCs). This qualitative and quantitative technique permits identification of the phenomena proceeding within the different elements composing the cell and at their interfaces.In this study, the classical conducting glass substrate was replaced by a protected stainless steel (304 type) substrate as the counter-electrode (cathode) in dye-sensitized solar cells. Platinum was deposited at the substrate surface to optimize the charge transfer resistance of the electrode.After a few days of immersion in the electrolytic solution, stainless steel substrates coated with low thickness of Pt show pitting corrosion due to iodine. Defects in the Pt layer such as discontinuity of the film and micro-cracks may explain the corrosion of the stainless steel substrate. However the Pt layer degradation is retarded for thicker films. On the other hand, polished substrates show a better behaviour probably due to the elimination of the defects on the stainless steel surface.Electrolytic solution was optimized. For this, components such as 1-butyl-3-methylimidazolium iodide (BMII), guanidine thiocyanate (GT) and 4-tert-butylpyridine (TBP) were added. No corrosion phenomena on stainless steel 304 appeared within 3 days when TBP was added. This means that TBP acts as a corrosion inhibitor.A schematic equivalent circuit is also proposed.     

Determination of water uptake and diffusion of Cl ion in epoxy primer on aluminum alloys in NaCl solution by electrochemical impedance spectroscopy

The electrochemical impedance spectroscopy (EIS) of epoxy-coated aluminum alloy LY12 has been investigated during exposure to 3.5% NaCl solution. Using the continuous simulation of EIS by expanded general electrical model, the time-dependent impedance model of the alloy/coating/solution system was deduced. The results shown that the composite electrode displayed a barrier behavior before water and oxygen penetrated to alloy base. After water and oxygen reached the base, the impedance associated with corrosion of alloy base changed with the immersion time as following: (i) active corrosion period at the beginning (double-layer capacitance, C_dl, in parallel to the charge transfer resistance of electrochemical corrosion R_ct), (ii) impeding of the diffusion of corrosion production at the intermediate period as a result of the presence of coated film (a constant phase element Z_diff was additionally in series with R_ct), and (iii) appearance of the characteristic impedance related to Cl⁻ ion-participating reaction with alloy base at the later stage. From the linear part of ln C_c–t^0.5 curve in the early immersion stage, the apparent diffusion coefficient of water was obtained. The diffusion coefficient of water and Cl⁻ ion through the coating was also calculated by the required time for diffusion of permeation species through the coating to the metal interface obtained from the simulation of EIS data by which the occurrence of characteristic impedance element(s) corresponding to special species arrival can be determined.     

Evaluation of sub-micrometer parylene C films as an insulation layer using electrochemical impedance spectroscopy

We investigated the insulation performance of sub-micrometer parylene C films over time using electrochemical impedance spectroscopy (EIS). For this, interdigitated electrodes were fabricated and completely encapsulated with parylene C in thicknesses of 50, 100, 200, and 500 nm. The EIS was measured in phosphate buffered saline (PBS) solution under an accelerated aging condition at 90 °C over 45 days. To analyze the EIS data, the equivalent circuit models of coating at different stages of coating degradation were used and the lumped circuit parameters of the best fitted equivalent circuit model were extracted by curve fitting. The analysis of impedance using the equivalent circuit model and the FTIR measurements suggest that sub-micrometer parylene C coatings exhibited delamination resulting from water diffusion from the top surface as soon as being immersed in PBS solution, although the degree of delamination varied depending on the film thickness. The penetration of water through sub-micrometers thick parylene C films can occur as quickly as the film is in contact with solution, unlike for thicker coatings in several micrometers where water diffusion would be saturated before water reaches the bottom surface of the coating.     

Corrosion of steel under the defected coating studied by localized electrochemical impedance spectroscopy

Corrosion of steel under the defected coating in near-neutral pH solution was investigated by localized electrochemical impedance spectroscopy (LEIS) measurements. The LEIS response is dependent on the size of the defect. For small defects, e.g., less than 200 μm in diameter, localized corrosion process and mechanism of steel, as indicated by the measured LEIS plots, change with time. The diffusion process dominates the interfacial corrosion reaction, which is due to the block effect of the deposited corrosion product combined with the geometrical factor of a large coating thickness/defect width ratio. In the presence of a big defect, e.g., up to 1000 μm, the LEIS responses measured at the defect are always featured by a coating impedance in the high-frequency range and an interfacial corrosion reaction in the low-frequency range. The block effect of corrosion product does not apply due to the relatively open geometry. Conventional EIS measurements on a macroscopic-coated electrode reflect the “averaged” impedance results from both coating and defect. The information of the localized electrochemical corrosion processes and mechanisms at the small defect is lost, and the coating impedance information is “averaged” out when a big defect is contained. LEIS measurement provides an essential technique to characterize microscopically the local electrochemical corrosion reaction of steel under the defected coating.     

Using electrochemical impedance spectroscopy to predict the corrosion resistance of unexposed coated metal panels

The goal of the current work was to determine if electrochemical impedance spectroscopy (EIS) testing of a series of coated but unexposed metal panels could predict the corrosion results of other sections of the same coated panels that were subjected to both continuous and cyclic corrosion testing. Variables included metal, pretreatment, primer, and topcoat. EIS results were shown to be strongly dependent upon the time-of-residence in the electrochemical cell prior to commencement of testing, and to the choice of electrolyte used in the cell. Good correlations between EIS and corrosion testing were seen for topcoat effects, but not for pretreatment effects. EIS results appear to relate mostly to barrier properties rather than electrochemical properties of coatings. It is suggested that the variation seen in EIS solution resistance values (R_s) can be utilized to quantify total system error. Total error was estimated by three techniques: total R_s variation, panel replicate variation, and EIS reading replication. The three approaches yielded similar results: total error for equivalent circuit components expressed in log₁₀ form was on the order of 50%, expressed as percent standard deviation.     

Poly(glutamic acid) nanofibre modified glassy carbon electrode: Characterization by atomic force microscopy, voltammetry and electrochemical impedance

Glassy carbon electrodes (GCE) were modified with poly(glutamic acid) acid films prepared using three different procedures: glutamic acid monomer electropolymerization (MONO), evaporation of poly(glutamic acid) (PAG) and evaporation of a mixture of poly(glutamic acid)/glutaraldehyde (PAG/GLU). All three films showed good adherence to the electrode surface. The performance of the modified GCE was investigated by cyclic voltammetry and differential pulse voltammetry, and the films were characterized by atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS). The three poly(glutamic acid) modified GCEs were tested using the electrochemical oxidation of ascorbic acid and a decrease of the overpotential and the improvement of the oxidation peak current was observed. The PAG modified electrode surfaces gave the best results. AFM morphological images showed a polymeric network film formed by well-defined nanofibres that may undergo extensive swelling in solution, allowing an easier electron transfer and higher oxidation peaks.     

Electrochemical impedance spectroscopy evidence of dimethyl-silicon-oil enhancing O2 transport in a porous electrode

Faster oxygen transport is critical to guarantee reliable power output of polymer electrolyte membrane fuel cells (PEMFCs). In order to enhance oxygen transfer in a porous electrode especially in the case of water flooding, water-proof oil (dimethyl-silicon-oil (DMS)) was introduced into the conventional Pt/C electrode. Owing to the capability of electrochemical impedance spectroscopy (EIS) in discriminating individual contribution of ohmic, kinetic, and mass transport from all PEMFC processes, EIS was carried out to evaluate the effect of the DMS on the oxygen reduction reaction (ORR). The equivalent circuits corresponding to the EIS spectra were employed. The parameters in the equivalent circuits were obtained by curve fitting to the EIS spectra with the aid of the frequency response analysis software (FRA) attached in the electrochemical station Autolab PGSYAT302. The EIS analysis has shown that the introduction of DMS reduces the oxygen diffusion resistance as well as the charge transfer resistance in the flooded state. The single cell tests show that even in the case of normal operating condition the accumulated water with PEMFC operation also worsens the oxygen transfer in the conventional Pt/C gas diffusion electrode (GDE) with more and more water produced at the cathode. GDE containing DMS, which is defined as a flooding tolerant electrode (FTE), is fortunately quite good at alleviating water flooding. Success of the FTE in alleviating water flooding is ascribed to (1) its high oxygen transfer flux due to the higher solubility of oxygen in DMS than in water as long as parts of pores are occupied beforehand by DMS rather than by water, and (2) enhanced hydrophobic property of the FTE with DMS adsorption on the walls of the pores, which makes more hydrophobic pores be open to oxygen transport.     

Corrosion behaviour of Ti-6Al-7Nb and Ti-6Al-4V ELI alloys in the simulated body fluid solution by electrochemical impedance spectroscopy

The corrosion behaviour of Ti-6Al-7Nb and Ti-6Al-4V ELI (extra low interstitial) was investigated as a function of immersion hours in simulated body fluid (SBF) condition, utilizing potentiodynamic polarisation and electrochemical impedance spectroscopy (EIS) techniques. Polarisation experiments were conducted after 0, 120, 240 and 360 h of immersion in SBF solution. From the polarisation curves, very low current densities were obtained for Ti-6Al-7Nb alloy compared to Ti-6Al-4V ELI, indicating a formation of stable passive layer. Impedance spectra were represented in the form of Bode plots and it was fitted using a non-linear least square (NLLS) fitting procedure, in which it exhibited a two time constant system suggesting the formation of two layers. The surface morphology of the titanium alloys have been characterized by SEM and EDAX measurements.     

Adsorption of bovine serum albumin and fibrinogen on hydrophilicity-controllable surfaces of polypyrrole doped with dodecyl benzene sulfonate—A combined piezoelectric quartz crystal impedance and electrochemical impedance study

Combined measurements of piezoelectric quartz crystal impedance (PQCI) and electrochemical impedance (EI) were utilized to monitor in situ adsorption of two proteins (bovine serum albumin and fibrinogen) onto the hydrophilicity-controllable surfaces of polypyrrole (PPY) doped with dodecyl benzene sulfonate (DBS). Three of these polymer films, PPY/DBS-I, PPY/DBS-II and PPY/DBS-III, were obtained by galvanostatic electropolymerization of pyrrole in aqueous solutions containing 0.6, 1.2 and 2.0 mmol L⁻¹ sodium dodecyl benzene sulfonate (SDBS), respectively. The PPY/DBS-II obtained from electropolymerization of pyrrole in the presence of 1.2 mmol L⁻¹ SDBS (the critical micelle concentration of SDBS in aqueous solution, CMC) exhibited the greatest hydrophobicity, as suggested by contact angle measurement. And the saturation-adsorption amounts for both proteins were found to be greatest on the surface. The kinetics and adsorption mechanisms of both proteins adsorbed on these three surfaces were discussed. Langmuir and Freundlich models were used for explaining the adsorption behavior of proteins, giving that Langmuir model is better for bovine serum albumin (BSA) and both model are not so available for fibrinogen.     

Characterization by electrochemical impedance spectroscopy of magnetite nanoparticles supported on carbon paste electrode

Magnetite nanoparticles were supported on carbon paste electrode and characterized by low scan rate voltammetry and electrochemical impedance spectroscopy (EIS) to obtain mechanistic information related to its oxidation and reduction in acid media.The voltammograms showed only one reduction and one oxidation peak for the supported magnetite, which were attributed to formation of ferrous ion and ferric oxide, respectively. Both peaks are fairly wide, indicating complex mechanisms.Using EIS, a mechanism showing up to three time constants, capacitive all of them, was evidenced, both in anodic and cathodic domain. These were attributed to charge transfer at the highest frequencies, adsorption of generated species at intermediate frequencies, and proton adsorption at low frequencies. Discussion about the nature of the adsorbed species and the concerned mechanism for each domain is developed.     

Investigation of alkylamine self-assembled films on iron electrodes by SEM, FT-IR, EIS and molecular simulations

Alkylamine were used to form self-assembled films for the inhibition of the corrosion of iron in 0.5 M H₂SO₄ solution. The films were characterized by electrochemical impedance spectroscopy (EIS) and surface analysis techniques including SEM and FT-IR. EIS results indicate that the inhibition ability of these alkylamine self-assembled films depends on the immersion time and the alky chain length of the adsorbate. Both longer immersion time of the electrode in the solution and longer alky chain will result in stronger inhibition ability of the films. However, when the immersion time was increased over some critical point, the inhibition ability was almost invariable. Also when the chain length reached a certain degree such as 14 carbon atoms, the inhibition ability decreased on the contrary. The ability of the corrosion inhibition of the tetradecylamine and dodecylthiol mixed films improved remarkably comparing with the tetradecylamine or dodecylthiol single films. In addition, molecular simulation was used to discuss the adsorption mechanism and good agreement with electrochemical results was obtained.     

Study of passivation of Al and Al-Sn alloys in borate buffer solutions using electrochemical impedance spectroscopy

Properties of thin oxide films on Al and Al-Sn alloys (with Sn content of 0.02, 0.09, 0.20 and 0.40 wt.%) formed either naturally or anodically in borate buffer solutions were investigated by means of electrochemical impedance spectroscopy. Equivalent circuits have been proposed that completely illustrate the Al(Al-Sn alloy)/oxide film/electrolyte systems examined, and properties of oxide films were determined. The stability (thickness and resistance) of oxide films has been found to increase with increased Sn content in the alloy, with increased passivation potential, and with longer time of anodising. The increase in temperature of anodising significantly reduces impedance in systems observed.     

Electrochemical behaviour of PANi/polyurethane antifouling coating in salt water studied by electrochemical impedance spectroscopy

Electrochemical behaviour of polyaniline–polyurethane (PANi–PU) antifouling coating in 3.5 wt% NaCl is studied by electrochemical impedance spectroscopy (EIS). A thick coating (∼1 mm) of 10, 15 and 20% PANi in marine grade PU, is cast over corrosion resistant aluminium alloy 2024 and its impedance characteristics are measured by EIS and compared with neat PU. On addition of 10% PANi, the impedance of the coating drastically comes down from 10⁹ to 10⁷ Ω. 20% is the maximum processable amount of PANi for the selected PU system. The coatings are exposed to 3.5 wt% NaCl and its impedance characteristics are monitored as a function of time. Changes in the impedance characteristics of the systems were found to occur as a function of the exposure time in all cases, though their evolution with time showed marked differences with PANi content. Water sorption and break down frequency are derived from the experimental results and analysed.     

Electrochemical impedance spectroscopy (EIS) study of nano-alumina modified alkyd based waterborne coatings

A nano-composite coating was formed by dispersing nano-Al₂O₃ as pigments in different concentrations, to a specially developed alkyd based waterborne coating. The nano-Al₂O₃ based composite coatings were applied on mild steel substrate by dipping. The dispersion of particles in coating system was investigated by using SEM and AFM techniques. The effect of addition of these nano-pigments on the electrochemical behavior of the coating was investigated in 3.5% NaCl solution, using electrochemical impedance spectroscopy (EIS). It was found that coating modified with higher concentration of nano-Al₂O₃ particles showed comparatively better performance as it was evident from pore resistance (R_p) and coating capacitance (C_c) values after 30 days of exposure. In general, the study showed an improvement in the corrosion resistance of the nano-particle modified coatings as compared to the neat coating, confirming the positive effect of nano-particle addition in coatings.     

Corrosion of the stressed pipe steel in carbonate-bicarbonate solution studied by scanning localized electrochemical impedance spectroscopy

Corrosion of X-70 pipe steel as a function of stress distribution was investigated by scanning localized electrochemical impedance spectroscopy (LEIS) technique. The deformation-induced stress, if not sufficiently high, has an inhibitive effect on corrosion reaction, pitting occurrence and crack initiation in pipe steel under high-pH condition. Such an inhibitive effect is due to the enhanced generation of carbonate product and the resultant surface block effect at the stressed zones. The tensile and compressive stresses have identical effect on inhibition of dissolution and pitting of the steel. However, tensile stress enhances the steel dissolution more significantly than compressive stress, and thus, generates more carbonate product, resulting in higher localized impedance. Pits are easy to occur around the neutral axis of the U-bend specimen, where the steel deformation and the resultant stress are ignorable. For pipelines encountering non-uniform stress distribution, the role of stress in crack initiation is critically different. Scanning LEIS technique provides a promising method to map and characterize corrosion of the steel as a function of the stress distribution.