Impedance Analysis of Electrochemical Systems.

Interpretation of impedance spectroscopy data requires both a description of the chemistry and physics that govern the system and an assessment of the error structure of the measurement. The approach presented here includes use of graphical methods to guide model development, use of a measurement model analysis to assess the presence of stochastic and bias errors, and a systematic development of interpretation models in terms of the proposed reaction mechanism and physical description. Application to corrosion, batteries, and biological systems is discussed, and emerging trends in interpretation and implementation of impedance spectroscopy are presented.

Impedance Response of a Thin Film on an Electrode: Deciphering the Influence of the Double Layer Capacitance.

The different contributions of the interfacial capacitance are identified in the case of passive materials or thin protective coatings deposited on the electrode surface. The method is based on a graphical analysis of the EIS results to determine both the passive-film capacitance in the high-frequency domain and the double-layer capacitance in the low-frequency domain. The proposed analysis is shown to be independent of the physicochemical origins of the frequency dispersion of the interfacial capacitances which results, from an analysis point of view of the experimental results, in the use of a constant-phase element However, for a correct evaluation of the thin-film properties such as its thickness, the high-frequency data must be corrected for the double-layer contribution. In particular, it is shown that if the double-layer capacitance gives a frequency-dispersed response, it is necessary to correct the high-frequency part for the double-layer constant-phase elements. This is first demonstrated on synthetic data and then used for the determination of the thickness of thin oxide film formed on Al in neutral pH solution.

Characterization of damaged skin by impedance spectroscopy: chemical damage by dimethyl sulfoxide.

PURPOSE: To relate changes in the electrochemical impedance spectra to the progression and mechanism of skin damage arising from exposure to dimethyl sulfoxide (DMSO). METHODS: Electrochemical impedance spectra measured before and after human cadaver skin was treated with neat DMSO or phosphate buffered saline (control) for 1 h or less were compared with electrical circuit models representing two contrasting theories describing the progression of DMSO damage. Flux of a model lipophilic compound (p-chloronitrobenzene) was also measured. RESULTS: The impedance spectra collected before and after 1 h treatment with DMSO were consistent with a single circuit model; whereas, the spectra collected after DMSO exposure for 0.25 h were consistent with the model circuits observed before and after DMSO treatment for 1 h combined in series. DMSO treatments did not significantly change the flux of p-chloronitrobenzene compared to control. CONCLUSIONS: Impedance measurements of human skin exposed to DMSO for less than about 0.5 h were consistent with the presence of two layers: one damaged irreversibly and one unchanged. The thickness of the damaged layer increased proportional to the square-root of treatment time until about 0.5 h, when DMSO affected the entire stratum corneum. Irreversible DMSO damage altered the lipophilic permeation pathway minimally.

Characterization of damaged skin by impedance spectroscopy: mechanical damage.

PURPOSE: Electrochemical impedance spectroscopy is a convenient method that has been used to characterize skin barrier function, which affects drug delivery into and through the skin. The objective of this study was to relate changes in skin barrier function arising from mechanical damage to changes in the impedance spectra. These observations are compared in a companion paper to changes in chemically damaged skin. METHODS: Electrical impedance and the permeation of a non-polar compound were measured before and after human cadaver skin was damaged by needle puncture. RESULTS: The impedance responses of all skin samples were consistent with an equivalent circuit model with a resistor and constant phase element (CPE) in parallel. Pinhole-damaged skin exhibited a lower resistance pathway acting in parallel with the skin resistance without changing the CPE behavior. The characteristic frequency of the impedance scans determined after needle puncture increased by an amount that could be predicted. The flux of 4-cyanophenol increased by a small but significant amount that did not correlate with the hole resistance calculated under the assumption that the resistance of the surrounding skin did not change. CONCLUSIONS: Skin impedance measurements are sensitive to irreversible damage caused by exposure to puncture with a needle.

On the correlation between single-frequency impedance measurements and human skin permeability to water.

The objective of this study was to quantitatively compare measurements of tritiated water permeability with impedance determined at either 100 or 1000 Hz using an LCR databridge on the same pieces of skin. A previously published expression based on a simple circuit of a parallel resistor and constant phase element (CPE) was used to relate (RPARA) measured at different frequencies to the DC resistance (RskinA) and the steady-state skin permeability of tritiated water (kp). Using this analysis, kp and (RPARA) data from three laboratories were shown to be consistent with each other, and kp and (RskinA) estimated from (RPARA) were linearly correlated. Compared with urea and mannitol, which are known to permeate skin through a polar pathway, the value of kp for water was found to be about two times larger than expected for transport through only the polar pathway, suggesting an approximately equal contribution from the lipophilic pathway. Equations relating kp to (RPARA) and (RskinA) were used to compare on a consistent basis proposed tests for identifying and excluding damaged skin from chemical absorption studies. The criterion of 20 kΩ cm2 for (RskinA) corresponds to a tritiated water permeability of 3.2×10(-3) cm/h, which should exclude damaged skin without screening undamaged but higher permeability skin samples from study.

An interfacial and bulk charge transport model for dye-sensitized solar cells based on photoanodes consisting of core-shell nanowire arrays.

Dye-sensitized solar cells (DSSCs) based on ordered photoanode morphologies, such as nanotubes and nanowires, are widely gaining attention because these geometries are believed to enhance interfacial charge transfer and bulk charge transport. Unfortunately, experimental results have yet to show substantial improvement to conversion efficiency over nanoparticle-based DSSCs. A model is developed to characterize the performance of an idealized photoanode based on an ordered array of transparent conductive nanowires coated with an anatase titania shell. The role of the interfacial electric field in nanowire-based DSSCs is explored computationally by turning electron migration ON or OFF. The results show that back-reaction rates are most strongly influenced by the electric field. These electron loss mechanisms can be reduced by several orders of magnitude, leading to improvements in short-circuit current, open-circuit voltage, and fill factor.

Corrosion of tungsten microelectrodes used in neural recording applications.

In neuroprosthetic applications, long-term electrode viability is necessary for robust recording of the activity of neural populations used for generating communication and control signals. The corrosion of tungsten microwire electrodes used for intracortical recording applications was analyzed in a controlled bench-top study and compared to the corrosion of tungsten microwires used in an in vivo study. Two electrolytes were investigated for the bench-top electrochemical analysis: 0.9% phosphate buffered saline (PBS) and 0.9% PBS containing 30 mM of hydrogen peroxide. The oxidation and reduction reactions responsible for corrosion were found by measurement of the open circuit potential and analysis of Pourbaix diagrams. Dissolution of tungsten to form the tungstic ion was found to be the corrosion mechanism. The corrosion rate was estimated from the polarization resistance, which was extrapolated from the electrochemical impedance spectroscopy data. The results show that tungsten microwires in an electrolyte of PBS have a corrosion rate of 300-700 µm/yr. The corrosion rate for tungsten microwires in an electrolyte containing PBS and 30 mM H2O2 is accelerated to 10,000-20,000 µm/yr. The corrosion rate was found to be controlled by the concentration of the reacting species in the cathodic reaction (e.g. O2 and H2O2). The in vivo corrosion rate, averaged over the duration of implantation, was estimated to be 100 µm/yr. The reduced in vivo corrosion rate as compared to the bench-top rate is attributed to decreased rate of oxygen diffusion caused by the presence of a biological film and a reduced concentration of available oxygen in the brain.

A critical analysis of single-frequency LCR databridge impedance measurements of human skin.

Testing whether the barrier of skin samples has sufficient integrity for meaningful measurements of in-vitro chemical permeability is usually required when data are generated for regulatory purposes. Recently, skin integrity has been assessed using LCR databridge measurements, which are reported as resistances determined in either series (SER) or parallel (PAR) modes at a single frequency, typically 100 or 1000Hz. Measurements made at different combinations of mode and frequency are known to differ, although the skin literature reveals confusion over the meaning of these differences and the impact on the interpretation of integrity test results. Here, the theoretical meanings of resistance and capacitance measurements in PAR and SER mode are described and confirmed experimentally. SER-mode resistances are equal to the real part of the complex impedance; whereas, PAR-mode resistances are the inverse of the real part of the admittance. Capacitance measurements reported in SER and PAR modes are similar manipulations of the imaginary parts of the complex impedance and admittance. A large body of data from human cadaver skin is used to show that the PAR-mode resistance and SER-mode capacitance measured at 100Hz are sensitive to skin resistivity, which is the electrical measurement most closely related to skin integrity.