Experimental and Numerical Investigation into the Effect of Water Uptake on the Capacitance of an Organic Coating.

Water uptake by organic coating systems used for corrosion prevention on airframes is one of the principal contributors to the loss of barrier properties of the coating. We used equivalent circuit analyses of electrochemical impedance spectroscopy (EIS) data to track changes in coating layer capacitance for a two-layer coating system consisting of an epoxy primer and polyurethane topcoat immersed in NaCl solutions with different concentrations and temperatures. The capacitance curve exhibited two different response regions, consistent with the "two-stage kinetics" mechanisms for water uptake by the polymers. We tested several numerical diffusion models of water sorption and found the most successful to be one that varied the diffusion coefficient as a function of polymer type and immersion time and accounted for physical aging processes in the polymer. We employed the Brasher mixing law along with the water sorption model to estimate the coating capacitance as a function of water uptake. The predicted capacitance of the coating was found to be consistent with the capacitance obtained from the EIS data, which is consistent with theories that water uptake occurs via initial rapid transport followed by a much slower aging process. Thus, both these water uptake processes need to be considered when making EIS measurements to assess the state of a coating system.

Stress-Affected Oxygen Reduction Reaction Rates on UNS S13800 Stainless Steel.

This work investigates the previously unexplored impact of tensile stress on oxygen reduction reaction (ORR) kinetics of a precipitation-hardened, stainless-steel fastener material, UNS S13800. ORR is known to drive localized and galvanic corrosion in aircraft assemblies and greater understanding of this reaction on structural alloys is important in forecasting component lifetime and service requirements. The mechano-electrochemical behavior of UNSS13800 was examined using amperometry to measure the reduction current response to tensile stress. Mechanical load cycles within the elastic regime demonstrated reversible electrochemical current shifts under chloride electrolyte droplets that exhibited a clear potential dependence. Strain ramping produced current peaks with a strain rate dependence, which was distinct from the chronoamperometric shifts during static tensile load conditions. Finally, mechanistic insight into the dynamic and static responses was obtained by deoxygenation, which demonstrated ORR contributions that were distinct from other reductive processes.

Photocurrent mapping of 3D CdSe/CdTe windowless solar cells.

This paper details the use of scanning photocurrent microscopy to examine localized current collection efficiency of thin-film photovoltaic devices with in-plane patterning at a submicrometer length scale. The devices are based upon two interdigitated comb electrodes at the micrometer length scale prepatterned on a substrate, with CdSe electrodeposited on one electrode and CdTe deposited over the entire surface of the resulting structure by pulsed laser deposition. Photocurrent maps provide information on what limits the performance of the windowless CdSe/CdTe thin-film photovoltaic devices, revealing "dead zones" particularly above the electrodes contacting the CdTe which is interpreted as recombination over the back contact. Additionally, the impact of ammonium sulfide passivation is examined, which enables device efficiency to reach 4.3% under simulated air mass 1.5 illumination.

Tuning the gas sensing performance of single PEDOT nanowire devices.

This paper reports the synthesis and dopant dependent electrical and sensing properties of single poly(ethylenedioxythiophene) (PEDOT) nanowire sensors. Dopant type (i.e. polystyrenesulfonate (PSS(-)) and perchlorate (ClO(4)(-))) and solvent (i.e. acetonitrile and 1 : 1 water-acetonitrile mixture) were adjusted to change the conjugation length and hydrophilicity of nanowires which resulted in change of the electrical properties and sensing performance. Temperature dependent coefficient of resistance (TCR) indicated that the electrical properties are greatly dependent on dopants and electrolyte where greater disorder was found in PSS(-) doped PEDOT nanowires compared to ClO(4)(-) doped nanowires. Upon exposure to different analytes including water vapor and volatile organic compounds, these nanowire devices displayed substantially different sensing characteristics. ClO(4)(-) doped PEDOT nanowires from an acetonitrile bath show superior sensing responses toward less electronegative analytes and followed a power law dependence on the analyte concentration at high partial pressures. These tunable sensing properties were attributed to variation in the conjugation lengths, dopant type and concentration of the wires which may be attributed to two distinct sensing mechanisms: swelling within the bulk of the nanowire and work function modulation of Schottky barrier junction between nanowire and electrodes.

Amperometric microbial biosensor for p-nitrophenol using Moraxella sp.-modified carbon paste electrode.

An amperometric microbial biosensor for highly specific, sensitive and rapid quantitative determination of p-nitrophenol was developed. The biosensor takes advantage of the ability of Moraxella sp. to specifically degrade p-nitrophenol to hydroquinone, a more electroactive compound than p-nitrophenol. The electrochemical oxidation current of hydroquinone formed in biodegradation of p-nitrophenol was measured at Moraxella sp.-modified carbon paste electrode and correlated to p-phenol concentrations. The optimum response was realized by electrode constructed using 15 mg of dry cell weight per 1 g of carbon paste and operating at 0.3 V (versus Ag/AgCl reference) in pH 7.5, 20 mM sodium phosphate buffer. Operating at these optimum conditions the biosensor had excellent selectivity against phenol derivatives and was able to measure as low as 20 nM (2.78 ppb) p-nitrophenol with very good accuracy and reproducibility. The biosensor was stable for approximately 3 weeks when stored at 4 degrees C. The applicability of the biosensor to measure p-nitrophenol in lake water was demonstrated.