Raman and XRD study on brookite-anatase coexistence in cathodic electrosynthesized titania

Among the many methods developed for the synthesis of titanium dioxide, cathodic electrosynthesis has not received much attention because the resulting amorphous oxy-hydroxide matrix demands a further thermal annealing step to be transformed into crystalline titania. However, the possibility of filling deep recessed templates by the control of the solidliquid interface makes it a potentially suitable technique for the fabrication of porous scaffolds for photovoltaics and photocatalysis. Furthermore, a careful control of the crystallization process enables the growth of larger grains with lower density of grain boundaries, which act as electron traps that slow down electronic transport and promote charge recombination. In this report, well crystallized titania deposits were obtained by thermal annealing of amorphous deposits fabricated by cathodically assisted electrosynthesis on indium-tin oxide (ITO)substrates. The combined use of Raman spectroscopy and X-ray diffraction showed that the crystallization process is more intricate than previously assumed. It is shown that the amorphous matrix evolves into a rutile-free mixture of brookite and anatase at temperatures as low as 200 degrees C that persists up to 800 degrees C, when pure anatase dominates. The amount of brookite in the brookiteanatase mixture reaches a maximum at 400 degrees C. This very simple method for obtaining a brookiteanatase mixture and the ability to tune their proportions by thermal annealing is a promising alternative whose potential for solar cells and photocatalysis deserves a careful evaluation. Copyright (C) 2011 John Wiley & Sons, Ltd.

Titanium surface topography after brushing with fluoride and fluoride-free toothpaste simulating 10 years of use

Objectives: To conduct a controlled study contrasting titanium surface topography after procedures that simulated 10 years of brushing using toothpastes with or without fluoride. Methods: Commercially pure titanium (cp Ti) and Ti-6Al-4V disks (6 mm circle divide x 4 mm) were mirror-polished and treated according to 6 groups (n = 6) as a function of immersion (I) or brushing (B) using deionised water (W), fluoride-free toothpaste (T) and fluoride toothpaste (FT). Surface topography was evaluated at baseline (pretreatment) and post-treatment, using atomic force microscope in order to obtain three-dimensional images and mean roughness. Specimens submitted to immersion were submerged in the vehicles without brushing. For brushed specimens, procedures were conducted using a linear brushing machine with a soft-bristled toothbrush. Immersion and brushing were performed for 244 h. IFT and BFT samples were analysed under scanning electron microscope with Energy-Dispersive X-ray Spectroscopy (EDS). Pre and post-treatment values were compared using the paired Student T-test (alpha = .05). Intergroup comparisons were conducted using one-way ANOVA with Tukey post-test (alpha = .05). Results: cp Ti mean roughness (in nanometers) comparing pre and post-treatment were: IW, 2.29 +/- 0.55/2.33 +/- 0.17; IT, 2.24 +/- 0.46/2.02 +/- 0.38; IFT, 2.22 +/- 0.53/1.95 +/- 0.36; BW, 2.22 +/- 0.42/3.76 +/- 0.45; BT, 2.27 +/- 0.55/16.05 +/- 3.25; BFT, 2.27 +/- 0.51/22.39 +/- 5.07. Mean roughness (in nanometers) measured in Ti-6Al-4V disks (pre/post-treatment) were: IW, 1.79 +/- 0.25/2.01 +/- 0.25; IT, 1.61 +/- 0.13/1.74 +/- 0.19; IFT, 1.92 +/- 0.39/2.29 +/- 0.51; BW, 2.00 +/- 0.71/2.05 +/- 0.43; BT, 2.37 +/- 0.86/11.17 +/- 2.29; BFT, 1.83 +/- 0.50/15.73 +/- 1.78. No significant differences were seen after immersions (p > .05). Brushing increased the roughness of cp Ti and of Ti-6Al-4V (p < .01); cp Ti had topographic changes after BW, BT and BFT treatments whilst Ti-6Al-4V was significantly different only after BT and BTF. EDS has not detected fluoride or sodium ions on metal surfaces. Conclusions: Exposure to toothpastes (immersion) does not affect titanium per se; their use during brushing affects titanium topography and roughness. The associated effects of toothpaste abrasives and fluorides seem to increase roughness on titanium brushed surfaces. (C) 2012 Elsevier Ltd. All rights reserved.

Study of the oxygen vacancy influence on magnetic properties of Fe- and Co-doped SnO2 diluted alloys

Transition-metal (TM)-doped diluted magnetic oxides (DMOs) have attracted attention from both experimental and theoretical points of view due to their potential use in spintronics towards new nanostructured devices and new technologies. In the present work, we study the magnetic properties of Sn0.96TM0.04O2 and Sn0.96TM0.04O1.98(V (O))(0.02), where TM = Fe and Co, focusing in particular in the role played by the presence of O vacancies nearby the TM. The calculated total energy as a function of the total magnetic moment per cell shows a magnetic metastability, corresponding to a ground state, respectively, with 2 and 1 mu(B)/cell, for Fe and Co. Two metastable states, with 0 and 4 mu(B)/cell were found for Fe, and a single value, 3 mu(B)/cell, for Co. The spin-crossover energies (E (S)) were calculated. The values are E (S) (0/2) = 107 meV and E (S) (4/2) = 25 meV for Fe. For Co, E (S) (3/1) = 36 meV. By creating O vacancies close to the TM site, we show that the metastablity and E (S) change. For iron, a new state appears, and the state with zero magnetic moment disappears. The ground state is 4 mu(B)/cell instead of 2 mu(B)/cell, and the energy E (S) (2/4) is 30 meV. For cobalt, the ground state is then found with 3 mu(B)/cell and the metastable state with 1 mu(B)/cell. The spin-crossover energy E (S) (1/3) is 21 meV. Our results suggest that these materials may be used in devices for spintronic applications that require different magnetization states.

Ion-sensing properties of 1D vanadium pentoxide nanostructures

The application of one-dimensional (1D) V2O5 center dot nH(2)O nanostructures as pH sensing material was evaluated. 1D V2O5 center dot nH(2)O nanostructures were obtained by a hydrothermal method with systematic control of morphology forming different nanostructures: nanoribbons, nanowires and nanorods. Deposited onto Au-covered substrates, 1D V2O5 center dot nH(2)O nanostructures were employed as gate material in pH sensors based on separative extended gate FET as an alternative to provide FET isolation from the chemical environment. 1D V2O5 center dot nH(2)O nanostructures showed pH sensitivity around the expected theoretical value. Due to high pH sensing properties, flexibility and low cost, further applications of 1D V2O5 center dot nH(2)O nanostructures comprise enzyme FET-based biosensors using immobilized enzymes.

Vanadium and Titanium Mixed Oxide Films: Synthesis, Characterization and Application as Ion Sensor

Vanadium/titanium mixed oxide films were produced using the sol-gel route. The structural investigation revealed that increased TiO2 molar ratio in the mixed oxide disturbs the V2O5 crystalline structure and makes it amorphous. This blocks the TiO2 phase transformation, so TiO2 stabilizes in the anatase phase. In addition the surface of the sample always presents larger amounts of TiO2 than expected, revealing a concentration gradient along the growth direction. For increased TiO2 molar ratios the roughness of the surface is reduced. Ion sensors were fabricated using the extended gate field effect transistor configuration. The obtained sensitivities varied in the range of 58 mV/pH down to 15 mV/pH according to the composition and morphology of the surface of the samples. Low TiO2 amounts presented better sensing properties that might be related to the cracked and inhomogeneous surfaces. Rising the TiO2 quantity in the films produces homogeneous surfaces but diminishes their sensitivities. Thus, the present paper reveals that the compositional and structural aspects change the surface morphology and electrical properties accounting for the final ion sensing properties of the V2O5/TiO2 films. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.053206jes] All rights reserved.

Electrochromic Properties of a Metallo-supramolecular Polymer Derived from Tetra(2-pyridyl-1,4-pyrazine) Ligands Integrated in Thin Multilayer Films

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C-1 at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.

First-principles studies of complex magnetism in Mn nanostructures on the Fe(001) surface

The magnetic properties of Mn nanostructures on the Fe(001) surface have been studied using the noncollinear first-principles real space-linear muffin-tin orbital-atomic sphere approximation method within density-functional theory. We have considered a variety of nanostructures such as adsorbed wires, pyramids, and flat and intermixed clusters of sizes varying from two to nine atoms. Our calculations of interatomic exchange interactions reveal the long-range nature of exchange interactions between Mn-Mn and Mn-Fe atoms. We have found that the strong dependence of these interactions on the local environment, the magnetic frustration, and the effect of spin-orbit coupling lead to the possibility of realizing complex noncollinear magnetic structures such as helical spin spiral and half-skyrmion.

Petrology and Sr-Nd characteristics of the Nova Lacerda dike swarm, SW Amazonian Craton: new insights regarding its subcontinental mantle source and Mesoproterozoic geodynamics

The NNW-trending Nova Lacerda tholeiitic dike swarm in Mato Grosso State, Central Brazil, intrudes the Nova Lacerda granite (1.46 Ga) and the Jauru granite-greenstone terrain (ca. 1.79-1.77 Ga). The swarm comprises diabases I and II and amphibolites emplaced at ca. 1.38 Ga. Geochemical data indicate that these are evolved tholeiites characterized by high LILE/HSFE and LREE/HSFE ratios. Isotopic modelling yields positive epsilon(Nd)(T) values (+0.86 to +2.65), whereas values for epsilon(Sr)(T) range from positive to negative (+1.96 to -5.56). Crustal contamination did not play a significant petrogenetic role, as indicated by a comparison of isotopic data (Sr-Nd) from both dikes and country rocks, and by the relationship between isotopic and geochemical parameters (SiO2, K2O, Rb/Sr, and La/Yb) of the dikes. We attribute the origin of these tholeiites to fractional crystallization of evolved melts derived from a heterogeneous mantle source. Comparison of the geochemical and isotopic data of the studied swarm and other tholeiitic Mesoproterozoic mafic intrusions of the SWAmazonian Craton the Serra da Providencia, Colorado, and Nova Brasilandia bimodal suites - indicates that parental melts of the Nova Lacerda swarm were derived from the most enriched mantle source. This enrichment was probably caused by the stronger influence of the EMI component on the DMM end-member. These data, coupled with trace element bulk-rock geochemistry of the country rocks, and comparisons with the Colorado Complex of similar age, suggest a continental-margin arc setting for the emplacement of the Nova Lacerda dikes.

Root niche separation can explain avoidance of seasonal drought stress and vulnerability of overstory trees to extended drought in a mature Amazonian forest

Large areas of Amazonian evergreen forest experience seasonal droughts extending for three or more months, yet show maximum rates of photosynthesis and evapotranspiration during dry intervals. This apparent resilience is belied by disproportionate mortality of the large trees in manipulations that reduce wet season rainfall, occurring after 2-3 years of treatment. The goal of this study is to characterize the mechanisms that produce these contrasting ecosystem responses. A mechanistic model is developed based on the ecohydrological framework of TIN (Triangulated Irregular Network)-based Real Time Integrated Basin Simulator + Vegetation Generator for Interactive Evolution (tRIBS+VEGGIE). The model is used to test the roles of deep roots and soil capillary flux to provide water to the forest during the dry season. Also examined is the importance of "root niche separation," in which roots of overstory trees extend to depth, where during the dry season they use water stored from wet season precipitation, while roots of understory trees are concentrated in shallow layers that access dry season precipitation directly. Observational data from the Tapajo's National Forest, Brazil, were used as meteorological forcing and provided comprehensive observational constraints on the model. Results strongly suggest that deep roots with root niche separation adaptations explain both the observed resilience during seasonal drought and the vulnerability of canopy-dominant trees to extended deficits of wet season rainfall. These mechanisms appear to provide an adaptive strategy that enhances productivity of the largest trees in the face of their disproportionate heat loads and water demand in the dry season. A sensitivity analysis exploring how wet season rainfall affects the stability of the rainforest system is presented. Citation: Ivanov, V. Y., L. R. Hutyra, S. C. Wofsy, J. W. Munger, S. R. Saleska, R. C. de Oliveira Jr., and P. B. de Camargo (2012), Root niche separation can explain avoidance of seasonal drought stress and vulnerability of overstory trees to extended drought in a mature Amazonian forest, Water Resour. Res., 48, W12507, doi:10.1029/2012WR011972.

Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

We describe the preparation of platinum nanoparticles (PtNPs) using the 3-n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl62- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen (E-pa = 0.1 V) and by the redox process of formation for PtO with E-pa = 1.3 V and E-pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (pi -> pi* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers (R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 x 10(-6) mol L-1 and a quantification limit (QL) of 8.6 x 10(-6) mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

Analysis of temperature variation influence on the analog performance of 45 degrees rotated triple-gate nMuGFETs

This work presents the analog performance of n-type triple-gate MuGFETs with high-k dielectrics and TiN gate material fabricated in 45 degrees rotated SOI substrates comparing their performance with standard MuGFETs fabricated without substrate rotation. Different fin widths are studied for temperatures ranging from 250 K up to 400 K. The results of transconductance, output conductance, transconductance over drain current ratio, intrinsic voltage gain and unit-gain frequency are studied. It is observed that the substrate rotation improves the carrier mobility of narrow MuGFETs at any temperature because of the changing in the conduction plane at the sidewalls from (1 1 0) to (1 0 0). For lower temperatures, the improvement of the carrier mobility of rotated MuGFETs is more noticeable as well as the rate of mobility improvement with the temperature decrease is larger. The output conductance is weakly affected by the substrate rotation. Although this improvement in the transconductance of rotated MuGFETs is negligibly transferred to the intrinsic voltage gain, the unity-gain frequency of rotated device is improved due to the larger carrier mobility in the entire range of temperatures studied. (C) 2011 Elsevier Ltd. All rights reserved.

Structural and mechanical analysis for the optimization of PVD oxide coatings for protection against metal dusting

The evolution of the structure and properties of Cr/Cr oxide thin films deposited on HK40 steel substrates by reactive magnetron sputtering (RMS) was investigated and linked to their potential protective behavior against metal dusting. Deposition time, mode of oxygen feeding, and application of bias voltage were varied to assess their effect on the density, adhesion, and integrity of the films. All the films showed a very fine columnar microstructure and the presence of amorphous Cr oxide. Both, an increasing time and a constant oxygen flow during deposition led to the development of relatively low density films and mud-like cracking patterns. A graded oxygen flow resulted in films with fewer cracks, but a careful control of the oxygen flow is required to obtain films with a truly graded structure. The effect of the bias voltage was much more significant and beneficial. An increasing negative bias voltage resulted in the development of denser films with a transition to an almost crack-free structure and better adhesion. The amorphous oxide resulted in low values of hardness and Young's modulus. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis and characterization of [Ru(eta(6)-C10H14)(dppf)X][PF6] (X = Cl, Br, I, SnF3) compounds: The X-ray structure of [Ru(eta(6)-C10H14)(dppf)Cl][SnCl3]center dot 0.45CH(2)Cl(2)

The arene-ruthenium complex [Ru(eta(6)-C10H14)(dppf)Cl]PF6 (1) was used as a precursor for the syntheses of the [Ru(eta(6)-C10H14)(dppf)Br]PF6 (2), [Ru(eta(6)-C10H14)(dppf)I]PF6 (3). [Ru(eta(6)-C10H14)(dppf)SnF3]PF6 (4) and [Ru(eta(6)-C10H14)(dppf)Cl][SnCl3]center dot 0.45CH(2)Cl(2) (5) complexes by its reactions with KBr, Kl, SnF2 and SnCl2. respectively. All of the compounds were characterized by NMR, IR, Fe-57 and Sn-119-Mossbauer spectroscopy, and cyclic voltammetry. The single-crystal X-ray structure analysis of the [Ru(eta(6)-C10H14)(dppf)Cl] [SnCl3]center dot 0.45CH(2)Cl(2) complex revealed the expected piano-stool geometry. Cyclic voltammograms of the complexes showed only one quasi-reversible electrochemical process, involving the oxidation of Fe(II) and Ru(II) at the same potential, which was confirmed by exhaustive electrolysis experiments. Fe-57-Mossbauer parameters obtained for the complexes (1-5) were fitted with one doublet corresponding to a site of one iron(II). The Sn-119-Mossbauer parameters of the complex (4) indicate that tin is tetra covalent. (c) 2012 Elsevier Ltd. All rights reserved.

A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF2+, SnCl2+, and SnO2+ using ab initio computer calculations. The ground states of SnF2+, SnCl2+, and SnO2+ are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF2+ dissociates into Sn2+ + F, the long range behaviour of the potential energy curves of SnCl2+ and SnO2+ is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T-e) to form SnF2+, SnCl2+, and SnO2+ from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO2+ and SnF2+ have been observed for prolonged oxygen (O-16(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF2) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl2+ has been detected for O-16(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl2) powder. To our knowledge, SnF2+ is a novel gas-phase molecule, whereas SnCl2+ had been detected previously by electron-impact ionization mass spectrometry, and SnO2+ had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4758475]

Behavioral driving through on line monitoring and activity-dependent stimulation in weakly electric fish

This work has been supported by Brazilian agencies FAPESP, CNPq, CAPES and grants MICINN BFU200908473 and TIN 201019607, SpanishBrazilian Cooperation PHB20070008 and 7ª Convocatoria De PROYECTOS de COOPERACION INTERUNIVERSITARIAUAMSANTANDER con America Latina