Electrochemistry in Room-Temperature Ionic Liquids: Potential Windows at Mercury Electrodes

The cathodic and anodic: potential limit of eleven different ionic liquids were determined at a mercury hemisphere electrode. Ionic liquids containing the phosphonium cation (tri(n-hexyl)tetradecylphosphonium, [P-14.6,P-6.6](+)) give the largest potential window, especially When Coupled to a trifluorotris(pentafluoroethyl)- [FAP](-). or bis(trifluoromethanesulfonyl)imide, [NTf2](-), anion.

Electrochemical Oxidation of Hydrogen Sulfide at Platinum Electrodes in Room Temperature Ionic Liquids: Evidence for Significant Accumulation of H2S at the Pt/1-Butyl-3-methylimidazolium Trifluoromethylsulfonate Interface

Electrochemical oxidation of hydrogen sulfide gas (H2S) has been studied at a platinum microelectrode (10 mu m diameter) in five room temperature ionic liquids (RTILs): [C(4)mim][OTf], [C(4)dmim][NTf2], [C(4)mim][PF6],. [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP] (where [C-n mim](+) = 1-alkyl-3-methylimidazolium, [C(n)dmim](+) = 1-alkyl-2,3-dimethylimidazolium, [P-14,P-6,P-6,P-6](+) = tris(p-hexyl)-tetradecylphosphonium, [OTf](-) = trifluoromethlysulfonate, [NTf2](-) = bis(trifluoromethylsulfonyl)imide, [PF6](-) = hexafluorophosphate, and [FAP](-) = trifluorotris(pentafluoroethyl)phosphate). In four of the RTILs ([C(4)dmim][NTf2], [C(4)mim][PF6], [C(6)mim][FAP], and [P-14,P-6,P-6,P-6][FAP]), no clear oxidative signal was observed. In [C(4)mim][OTf], a chemically irreversible oxidation peak was observed on the oxidative sweep with no signal seen on the reverse scan. The oxidative signal showed an adsorptive stripping peak type followed by near steady-state limiting current behavior. Potential step chronoamperometry was carried out on the reductive wave, giving a diffusion coefficient and solubility of 1.6 x 10(-11) m(2) s(-1) and 7 mM, respectively (at 25 degrees C). Using these data, we modeled the oxidation signal kinetically, assuming adsorption preceded oxidation and that adsorption was approximately Langmuirian. The oxidation step was described by an electrochemically fully irreversible Tafel law/Butler-Volmer formalism. Modeling indicated a substantial buildup of H2S in the double layer in excess of the coverage that would be expected for a monolayer of chemisorbed H2S, reflecting high solubility of the gas in [C(4)mim][OTf] and possible attractive interactions with the [OTf](-) anions accumulated at the electrode at potentials positive of the potential of zero charge. Solute enrichment of the double layer in the solution adjacent to the electrode appears a novel feature of RTIL electrochemistry.

Development and Longer Term In Situ Evaluation of Fiber-Optic Sensors for Monitoring of Structural Concrete

In this paper, new solutions to the problem of making measurements, of carbonation and chloride ingress, in particular, in concrete structures are considered. The approach has focused on the design, development, and use of fiber-optic sensors (FOSs), recognizing the need in that conventional devices are often either inaccurate, expensive, or unsuitable for encapsulation in the material. The sensors have been designed to monitor, in situ and nondestructively, relevant physical, and chemical changes in cementitious materials. Three different types of FOS were constructed, tested, and evaluated specifically for this application, these being a temperature sensor (based on the fluorescence decay) and pH and chloride sensors, based on sol-gel (solidified gel) technology with appropriate impregnated indicators. The sensors were all designed to be inserted into the structures and evaluated under the harshest conditions, i.e., being mounted when the mortar is poured and thus tested in situ, with the temperature and pH sensors successfully embedded in mortar. The outcomes of these tests have shown that both the temperature sensor and the pH sensor were able to function correctly for the duration of the work - for over 18 months after placement. The laboratory tests on the chloride sensor showed it was able to make measurements but was not reversible, limiting its potential utility for in situ environments. Research is ongoing to refine the sensor performance and extend the testing.

Monitoring microbial sulfate reduction in porous media using multi-purpose electrodes

There is growing interest in the application of electrode-based measurements for monitoring microbial processes in the Earth using biogeophysical methods. In this study, reactive electrode measurements were combined to electrical geophysical measurements during microbial sulfate reduction occurring in a column of silica beads saturated with natural river water. Electrodic potential (EP), self potential (SP) and complex conductivity signals were recorded using a dual electrode design (Ag/AgCl metal as sensing/EP electrode, Ag/AgCl metal in KCl gel as reference/SP electrode). Open-circuit potentials, representing the tendency for electrochemical reactions to occur on the electrode surfaces, were recorded between sensing/EP electrode and reference/SP electrode and showed significant spatiotemporal variability associated with microbial activity. The dual electrode design isolates the microbial driven sulfide reactions to the sensing electrode and permits removal of any SP signal from the EP measurement. Based on the known sensitivity of a Ag electrode to dissolved sulfide, we interpret EP signals exceeding 550 mV recorded in this experiment in terms of bisulfide (HS-) concentration near multiple sensing electrodes. Complex conductivity measurements capture an imaginary conductivity (s?) signal interpreted as the response of microbial growth and biomass formation in the column. Our results suggest that the implementation of multipurpose electrodes, combining reactive measurements with electrical geophysical measurements, could improve efforts to monitor microbial processes in the Earth using electrodes.

The effect of 3D weaving and consolidation on carbon fiber tows, fabrics, and composites

This article investigates the damage imparted on load-bearing carbon fibers during the 3D weaving process and the subsequent compaction behavior of 3D woven textile preforms. The 3D multi-layer reinforcements were manufactured on a textile loom with few mechanical modifications to produce preforms with fibers orientated in the warp, weft, and through-the-thickness directions. Tensile tests were conducted on three types of commercially available carbon fibers, 12k HTA, 6k HTS, and 3k HTS in an attempt to quantify the effect of fiber damage induced during the 3D weaving process on the mechanical and physical performance of the fiber tows in the woven composite. The tests were conducted on fiber tows sampled from different locations in the manufacturing process from the bobbin, through the creel and loom mechanism, to the final woven fabric. Mechanical and physical testing were then conducted to quantify the tow geometry, orientation and the effect of compaction during manufacture of two styles of 3D woven composite by vacuumassisted resin transfer molding (VaRTM).