Effects of Chromate and Chromate Conversion Coatings on Corrosion of Aluminum Alloy 2024-T3

Various effects of chromate conversion coatings (CCCs) and chromate in solution on the corrosion of AA2024-T3 and pure Al are studied in this work. Raman spectroscopy was used to investigate the nature of chromate in CCCs through a comparison with the spectra of known standards and artificial Cr(III)/Cr(VI) mixed oxides. Chromate was shown to be released from CCCs and to migrate to and protect a nearby, uncoated area in the artificial scratch cell. However, experiments investigating the effect of chromate in solution on anodic dissolution kinetics under potentiostatic control indicated that large chromate concentrations were needed to have an effect.This work was supported by Major H. DeLong at the United States Air Force Office of Scientific Research under contracts F49620-96-1-0479 and F49620-96-0042

Scanning Electrochemical Microscopy. Theory of the Feedback Mode

The steady-state current that flows between the scanning tlp (a disk ultramicroelectrode imbedded in an Insulating sheath) and a planar sample substrate in a scannlng electrochemical microscope (SECM) operating in the feedback mode is calculated by the finite element method with an exponentlaily expandlng grld, for both conductlve and Insulating samples. For conductlve substrates the tip current, representing, for example, the oxidatkn reactlon of R to 0, is enhanced by flow of R generated at the substrate to the tlp and is a functlon of tiphubstrate distance, d , but not the radius of the lnsuiatlng sheath. For insulating substrates, the tlp current Is decreased by blockage of the diffusion of R to the tip by the substrate and depends upon d and the Insulating sheath radius. The theoretical results are compared to experimental studies

Raman Optical Activity Using Twisted Photons

Raman optical activity underpins a powerful vibrational spectroscopic technique for obtaining detailed structural information about chiral molecular species. The effect centers on the discriminatory interplay between the handedness of material chirality with that of circularly polarized light. Twisted light possessing an optical orbital angular momentum carries helical phase fronts that screw either clockwise or anticlockwise and, thus, possess a handedness that is completely distinct from the polarization. Here a novel form of Raman optical activity that is sensitive to the handedness of the incident twisted photons through a spin-orbit interaction of light is identified, representing a new chiroptical spectroscopic technique

Electronic Characteristics and Charge Transport Mechanisms for Large Area Aromatic Molecular Junctions

This paper reports the electron transport characteristics of carbon/molecule/Cu molecular junctions, where aromatic molecules (azobenzene or AB and nitroazobenzene or NAB) are employed as the molecular component. It is shown that these devices can be made with high yield (>90%), display excellent reproducibility, and can withstand at least 1.5 × 10 9 potential cycles and temperatures of at least 180°C. Transport mechanisms are investigated by analysis of current density/voltage (J-V) curves as a function of the molecular layer thickness and temperature. Results show that J decreases exponentially with thickness, giving a measured value for the low-bias attenuation factor ( ) of 2.5 ( 0.1 nm -1 for AB and NAB. In addition, it is shown that transport is not thermally activated over a wide range of temperatures (5-450 K) and that the appearance of a thermally "activated" region at higher temperatures can be accounted for by the effect of temperature on the distribution of electrons around the Fermi level of the contact(s). These results indicate that quantum mechanical tunneling is likely the mechanism for charge transport in these junctions. Although application of the Simmons tunneling model leads to transport parameters consistent with nonresonant tunneling, the parameters obtained from fitting experimental data indicate that the barrier height and/or shape, effective mass, and dielectric constant (ε) can all change with thickness. Experimental measurements of ε and density functional theory (DFT) calculations of molecular energy levels and polarizability support these conclusions. Finally, the implications of the transport mechanisms are discussed from the viewpoint of designing functional molecular electronic devices

Pseudo-single crystal electrochemistry on polycrystalline electrodes : visualizing activity at grains and grain boundaries on platinum for the Fe2+/Fe3+ redox reaction

The influence of electrode surface structure on electrochemical reaction rates and mechanisms is a major theme in electrochemical research, especially as electrodes with inherent structural heterogeneities are used ubiquitously. Yet, probing local electrochemistry and surface structure at complex surfaces is challenging. In this paper, high spatial resolution scanning electrochemical cell microscopy (SECCM) complemented with electron backscatter diffraction (EBSD) is demonstrated as a means of performing ‘pseudo-single-crystal’ electrochemical measurements at individual grains of a polycrystalline platinum electrode, while also allowing grain boundaries to be probed. Using the Fe2+/3+ couple as an illustrative case, a strong correlation is found between local surface structure and electrochemical activity. Variations in electrochemical activity for individual high index grains, visualized in a weakly adsorbing perchlorate medium, show that there is higher activity on grains with a significant (101) orientation contribution, compared to those with (001) and (111) contribution, consistent with findings on single-crystal electrodes. Interestingly, for Fe2+ oxidation in a sulfate medium a different pattern of activity emerges. Here, SECCM reveals only minor variations in activity between individual grains, again consistent with single-crystal studies, with a greatly enhanced activity at grain boundaries. This suggests that these sites may contribute significantly to the overall electrochemical behavior measured on the macroscale

Carbon stable isotope analysis of cereal remains as a way to reconstruct water availability: preliminary results

Reconstructing past water availability, both as rainfall and irrigation, is important to answer questions about the way society reacts to climate and its changes and the role of irrigation in the development of social complexity. Carbon stable isotope analysis of archaeobotanical remains is a potentially valuable method for reconstructing water availability. To further define the relationship between water availability and plant carbon isotope composition and to set up baseline values for the Southern Levant, grains of experimentally grown barley and sorghum were studied. The cereal crops were grown at three stations under five different irrigation regimes in Jordan. Results indicate that a positive but weak relationship exists between irrigation regime and total water input of barley grains, but no relationship was found for sorghum. The relationship for barley is site-specific and inter-annual variation was present at Deir ‘Alla, but not at Ramtha and Khirbet as-Samra

Electrocatalytic performance of SiO2-SWCNT nanocomposites prepared by electroassisted deposition

“The final publication is available at Springer via http://dx.doi.org/10.1007/s12678-013-0144-3”Composite materials made of porous SiO2 matrices filled with single-walled carbon nanotubes (SWCNTs) were deposited on electrodes by an electroassisted deposition method. The synthesized materials were characterized by several techniques, showing that porous silica prevents the aggregation of SWCNT on the electrodes, as could be observed by transmission electron microscopy and Raman spectroscopy. Different redox probes were employed to test their electrochemical sensing properties. The silica layer allows the permeation of the redox probes to the electrode surface and improves the electrochemical reversibility indicating an electrocatalytic effect by the incorporation of dispersed SWCNT into the silica films.This work was financed by the following research projects: MAT2010-15273 of the Spanish Ministerio de Economia y Competitividad and FEDER, PROMETEO/2013/038 of the GV, and CIVP16A1821 of the Fundacion Ramon Areces. Alonso Gamero-Quijano and David Salinas-Torres acknowledge Generalitat Valenciana (Santiago Grisolia Program) and Ministerio de Economia y Competitividad, respectively, for the funding of their research fellowships.Gamero-Quijano, A.; Huerta, F.; Salinas-Torres, D.; Morallón, E.; Montilla, F. (2013). Electrocatalytic performance of SiO2-SWCNT nanocomposites prepared by electroassisted deposition. Electrocatalysis. 4(4):259-266. https://doi.org/10.1007/s12678-013-0144-3S25926644P. Alivisatos, Nat. Biotechnol. 22, 47 (2004)S. Stankovich, D.A. Dikin, G.H. Dommett, K.M. Kohlhaas, E.J. Zimney, E.A. Stach, R.D. Piner, S.T. Nguyen, R.S. Ruoff, Nature 442, 282 (2006)D.W. Schaefer, R.S. Justice, Macromolecules 40, 8501 (2007)M. Endo, M.S. Strano, P.M. Ajayan, Carbon Nanotubes 111, 13 (2008)C.E. Banks, R.G. Compton, Analyst 131, 15 (2006)R.H. Baughman, A.A. Zakhidov, W.A. de Heer, Science 297, 787 (2002)Y.H. Lin, F. Lu, Y. Tu, Z.F. Ren, Nano Letters 4, 191 (2004)B.R. Azamian, J.J. Davis, K.S. Coleman, C.B. Bagshaw, M.L.H. Green, J. Am. Chem. Soc. 124, 12664 (2002)W. Yang, K. Ratinac, S. Ringer, P. Thordarson, J.G. Gooding, F. Braet, Angew. Chem. Int. Ed. 49, 2114 (2010)C.E. Banks, R.G. Compton, Analyst 130, 1232 (2005)L. Mazurenko, M. Etienne, O. Tananaiko, V. Zaitsev, A. Walcarius, Electrochim. Acta 83, 359 (2012)J.M.P. Paloma Yáñez-Sedeño, J. Riu, F.X. Rius, TrAC Trends in Analytical Chemistry 29, 939 (2010)Z.J. Wang, M. Etienne, S. Poller, W. Schuhmann, G.W. Kohring, V. Mamane, A. Walcarius, Electroanalysis 24, 376 (2012)R. Bandyopadhyaya, E. Nativ-Roth, O. Regev, R. Yerushalmi-Rozen, Nano Letters 2, 25 (2002)C. Park, Z. Ounaies, K.A. Watson, R.E. Crooks, J. Smith, S.E. Lowther, J.W. Connell, E.J. Siochi, J.S. Harrison, T.L.S. Clair, Chem. Phys. Lett. 364, 303 (2002)O. Matarredona, H. Rhoads, Z.R. Li, J.H. Harwell, L. Balzano, D.E. Resasco, Journal of Physical Chemistry B 107, 13357 (2003)L. Vaisman, H. Wagner, G. Marom, Advances in Colloid and Interface Science 128, 37 (2006)Y.C. Xing, Journal of Physical Chemistry B 108, 19255 (2004)J.J. Liang, Y. Huang, L. Zhang, Y. Wang, Y.F. Ma, T.Y. Guo, Y.S. Chen, Adv. Funct. Mater. 19, 2297 (2009)D. Salinas-Torres, F. Huerta, F. Montilla, E. Morallón, Electrochim. Acta 56, 2464 (2011)Z.F. Ren, Z.P. Huang, J.W. Xu, J.H. Wang, P. Bush, M.P. Siegal, P.N. Provencio, Science 282, 1105 (1998)W.Z. Li, S.S. Xie, L.X. Qian, B.H. Chang, B.S. Zou, W.Y. Zhou, R.A. Zhao, G. Wang, Science 274, 1701 (1996)M. Terrones, N. Grobert, J. Olivares, J.P. Zhang, H. Terrones, K. Kordatos, W.K. Hsu, J.P. Hare, P.D. Townsend, K. Prassides, A.K. Cheetham, H.W. Kroto, D.R.M. Walton, Nature 388, 52 (1997)R. Toledano, D. Mandler, Chem. Mater. 22, 3943 (2010)J.H. Rouse, Langmuir 21, 1055 (2005)X.B. Yan, B.K. Tay, Y. Yang, Journal of Physical Chemistry B 110, 25844 (2006)J. Lim, P. Malati, F. Bonet, B. Dunn, J. Electrochem. Soc. 154, A140 (2007)L.D. Zhu, C.Y. Tian, J.L. Zhai, R.L. Yang, Sensors and Actuators B-Chemical 125, 254 (2007)F. Montilla, M.A. Cotarelo, E. Morallón, J. Mater. Chem. 19, 305 (2009)D. Salinas-Torres, F. Montilla, F. Huerta, E. Morallón, Electrochim. Acta 56, 3620 (2011)T. Dobbins, R. Chevious, Y. Lvov, Polymers 3, 942 (2011)R. Esquembre, J.A. Poveda, C.R. Mateo, Journal of Physical Chemistry B 113, 7534 (2009)M.L. Ferrer, R. Esquembre, I. Ortega, C.R. Mateo, F. del Monte, Chem. Mater. 18, 554 (2006)M.J. O'Connell, S. Sivaram, S.K. Doorn, Physical Review B 69, 235415 (2004)C. Domingo, G. Santoro, Opt. Pura Apl 40, 175 (2007)M.S. Dresselhaus, G. Dresselhaus, R. Saito, A. Jorio, Physics Reports 409, 47 (2005)R.L. McCreery, Chem. Rev. 108, 2646 (2008)C.G. Zoski, in Handbook of Electrochemistry, 1st ed (Elsevier, Amsterdam, 2007

Advanced Computational Thermal Fluid Physics (CTFP) and Its Assessment for Light Water Reactors and Supercritical Reactors

Background: The ultimate goal of the study is the improvement of predictive methods for safety analyses and design of Generation IV reactor systems such as supercritical water reactors (SCWR) for higher efficiency, improved performance and operation, design simplification, enhanced safety and reduced waste and cost. The objective of this Korean / US / laboratory / university collaboration of coupled fundamental computational and experimental studies is to develop the supporting knowledge needed for improved predictive techniques for use in the technology development of Generation IV reactor concepts and their passive safety systems. The present study emphasizes SCWR concepts in the Generation IV program