Electrochemical Control of the Time-Dependent Intensity Fluctuations in Surface-Enhanced Raman Scattering (SERS)

Time-dependent fluctuations in surface-enhanced Raman scattering (SERS) intensities were recorded from a roughened silver electrode immersed in diluted solutions of rhodamine 6G (R6G) and congo red (CR). These fluctuations were attributed to a small number of SERS-active molecules probing regions of extremely high electromagnetic field (hot spots) at the nanostructured surface. The time-dependent distribution of SERS intensities followed a tailed statistics at certain applied potentials, which has been linked to single-molecule dynamics. The shape of the distribution was reversibly tuned by the applied voltage. Mixtures of both dyes, R6G and CR, at low concentrations were also investigated. Since R6G is a cationic dye and CR is an anionic dye, the statistics of the SERS intensity distribution of either dye in a mixture were independently controlled by adjusting the applied potential. The potential-controlled distribution of SERS intensities was interpreted by considering the modulation of the surface coverage of the adsorbed dye by the interfacial electric field. This interpretation was supported by a two-dimensional Monte Carlo simulation that took into account the time evolution of the surface configuration of the adsorbed species and their probability to populate a hypothetical hot spot. The potential-controlled SERS dynamics reported here is a first step toward the spectroelectrochemical investigation of redox processes at the single-molecule level by SERS.

Surface-Enhanced Resonance Raman Scattering of Polyaniline on Silver and Gold Colloids

The interaction of emeraldine base (PANI-EB) with silver and gold colloids was probed by using Surface-Enhanced Resonance Raman Scattering (SERRS) at 3 different exciting radiations. Due to the great sensitivity of SERRS technique the detection limit of PANI-EB concentration was ca. 2 x 10(-7) mol L(-1) in Ag and Au colloidal suspensions. The UV-vis-NIR spectra of metal colloids in function of PANI-EB concentrations showed that gold colloids present a higher degree of aggregation than silver colloids. SERRS of PANI-EB on metal colloids allowed the study of the polymeric species formed primarily on the metallic surface. The polymer formed after the adsorption of PANI-EB on metallic nanoparticles is strongly dependent on the nature of the metal colloids. The oxidation of PANI-EB to pernigraniline occurred for silver colloids, while a doping process of PANI-EB on Au nanoparticles was evidenced through the observation of the characteristic SERRS spectrum of emeraldine salt at 1064nm.

Evidence for diffusional coupling in electrochemical thin layers: implications for surface coverage calibration via electrochemical infrared spectroscopy

The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1-3 min). However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage calibration using solution-phase species is proposed.

A surface-enhanced infrared absorption spectroscopic (SEIRAS) study of the oscillatory electro-oxidation of methanol on platinum

The oscillatory electro-oxidation of methanol was studied by means of in situ infrared (IR) spectroscopy in the attenuated total reflection (ATR) configuration using a platinum film on a Si prism as working electrode. The surface-enhanced infrared absorption (SEIRA) effect considerably improves the spectroscopic resolution, allowing at following the coverage of some adsorbing species during the galvanostatic oscillations. Carbon monoxide was the main adsorbed specie observed in the induction period and within the oscillatory regime. The system was investigated at two distinct time-scales and its dynamics characterized accordingly. During the induction period the main transformation observed as the system move through the phase space towards the oscillatory region was the decrease of the coverage of adsorbed carbon, coupled to the increase of the electrode potential. Similar transition characterizes the evolution within the oscillatory region, but at a considerably slower rate. Experiments with higher time resolution revealed that the electrode potential oscillates in-phase with the frequency of the linearly adsorbed CO vibration and that the amount of adsorbed CO oscillates with small amplitude. Adsorbed formate was found to play, if any, a very small role. Results are discussed and compared with other systems. (C) 2010 Elsevier B.V. All rights reserved.

Behaviour of Surface Defects in Wire Rod Rolling

Defects are often present in rolled products, such as wire rod. The markets demand for wire rod without any defects has increased. In the final wire rod products, defects originating from the steel making, casting, pre-rolling of billets and during the wire rod rolling can appear. In this work, artificial V-shaped longitudinal surface cracks has been analysed experimentally and by means of FEM. The results indicate that the experiments and FEM calculations show the same tendency except in two cases, where instability due to a fairly “round” false round bars disturbed the experiment. FE studies in combination with practical experiments are necessary in order to understand the behaviour of the material flows in the groove and to explain whether the crack will open up as a V-shape or if it will be closed as an I-shape.

Monitoring Surface Displacement of the Colby Green Retaining Pond Dams

The Colby Green is a campus expansion project which began in October of 2003. The construction would result in three new buildings, additional parking, and an elliptical 75,000-squarefoot green southeast of Mayflower Hill Drive. There were also plans for the construction of three run-off management and sediment ponds below the green, to manage flooding of the green. Three drains in the green transport water to the three retaining ponds which slowly disperse water into the surrounding environment. The ponds were created by constructing earthen dams around the drain outlets. The dams are composed of soil, cobbles, and boulders procured from the surrounding excavation site. Unfortunately, earthen dams are susceptible to many types of erosion which result in their failure. In this case the potential for clay and silt from the underlying Presumpscot Formation to mix with the soil in the earthen dams raised concerns with regards to frost action. In order to monitor the surface displacement of the dams I drove 92 poles into the ground in 8 straight lines across the faces of the dams in the fall of 2005. I returned to the sites during and after the spring thaw of 2006, to check for any signs of movement resulting from frost-heave, surface creep, or any other form of mass wasting. Fortunately, there was no recordable sign of movement in the stakes across any of the retaining ponds. The dams appear to be functioning as designed.