Sn(1-x)LaxO2 thin films deposited on AISI 304 stainless steel substrates

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Electrocatalytic effect of Pb and Sn adatoms on the oxidation of 1-propanol on platinized platinum electrodes: Determination of the apparent activation energy

The electrocatalytic oxidation of 1-propanol was investigated on platinum electrodes modified by submonolayers of Pb and Sn in acid media. An increase of oxidation rates observed for both Pb and Sn, and the influence of theta values was investigated. The values of the apparent activation energy evaluated from the Arrhenius plots concerning the electrochemical oxidation of 1-propanol on modified platinzed platinum electrodes, reveal a significant decrease in the presence of upd Sn and Ph adatoms. A decrease from 56 to 26 U mol(-1) in the presence of Sn. and from 78 to 25 U mol(-1) for Ph adatoms are some illustrative values which reflect the promoting effect of the upd adatoms.

Aplicação de métodos computacionais no estudo das fases intermetálicas ordenadas pt-sn

Fuel cells are a very promising solution to the problems of power generation and emission of pollutant to the environment, excellent to be used in stationary application and mobile application too. The high cost of production of these devices, mainly due to the use of noble metals as anode, is a major obstacle to massive production and deployment of this technology, however the use of intermetallic phases of platinum combined with other metals less noble has been evaluated as electrodes in order to minimize production costs and still being able to significantly improve the catalytic performance of the anode. The study of intermetallic phases, exclusively done by experimental techniques is not complete and demand that other methods need to be applied to a deeper understanding of the behavior geometric properties and the electronic structure of the material, to this end the use of computer simulation methods, which have proved appropriate for a broader understanding of the geometric and electronic properties of the materials involved, so far not so well understood.. The use of computational methods provides answers to explain the behavior of the materials and allows assessing whether the intermetallic may be a good electrode. In this research project was used the Quantum-ESPRESSO package, based on the DFT theory, which provides the self-consistent field calculations with great precision, calculations of the periodic systems interatomic force, and other post-processing calculations that points to a knowledge of the geometric and electronic properties of materials, which may be related to other properties of them, even the electrocatalytic. The electronic structure is determined from the optimized geometric structure of materials by analyzing the density of states (DOS) projected onto atomic orbital, which determines the influence of the electrocatalytic properties of the material... (Complete abstract click electronic access below)

The effect of alloying in Pt-Sn/C electrocatalysts in the performance of a direct ethanol fuel cell

Work on Pt-Sn-C catalysts for ethanol oxidation showed that a thermal treatment at moderate temperatures leads to a significant increase in activity. The best activity was observed for Pt3Sn1 thermally treated at 200 degrees C and ascribed to a Pt3Sn1 phase plus a cleaning effect. However, electronic effects may be very important and these were not evaluated in the Pt3Sn1 phase. Therefore, in this work we investigated the effect of the degree of alloy on the electronic structure of Pt3Sn1 electrocatalysts by performing electrochemical in situ X-ray absorption (XAS) experiments in the Pt L-III XANES region. Overall, the results show that although the occupancy of the Pt 5d band depends on the degree of alloy other factors, such as the presence of tin oxides/hydroxides in the materials, have to be considered to understand the performance of the DEFC.

Structure, microstructure, and selected mechanical properties of Ti-Zr-Mo alloys for biomedical applications

New titanium alloys for biomedical applications have been developed primarily with the addition of Nb, Ta, Mo, and Zr, because those elements stabilize the β phase and they don’t cause cytotoxicity in the organism. The objective of this paper is to analyze the effect of molybdenum on the structure, microstructure, and selected mechanical properties of Ti-15Zr-xMo (x = 5, 10, 15, and 20 wt%) alloys. The samples were produced in an arc-melting furnace with inert argon atmosphere, and they were hot-rolled and homogenized. The samples were characterized using chemical, structural, and microstructural analysis. The mechanical analysis was made using Vickers microhardness and Young’s modulus measurements. The compositions of the alloys were sensitive to the molybdenum concentration, indicating the presence of α’+α”+β phases in the Ti-15Zr-5Mo alloy, α”+β in the Ti-15Zr-10Mo alloy, and β phase in the Ti-15Zr-15Mo and Ti-15Zr-20Mo alloys. The mechanical properties showed favorable values for biomedical application in the alloys presenting high hardness and low Young’s modulus compared with CP-Ti.

Effect of the substitutional elements on the microstructure of the Ti-15Mo-Zr and Ti-15Zr-Mo systems alloys

Titanium alloys have excellent biocompatibility, and combined with their low elastic modulus, become more efficient when applied in orthopedic prostheses. Samples of Ti-15Mo-Zr and Ti-15Zr-Mo system alloys were prepared using an arc-melting furnace with argon atmosphere. The chemical quantitative analysis was performed using an optical emission spectrometer with inductively coupled plasma and thermal conductivity difference. The X-ray diffractograms, allied with optical microscopy, revealed the structure and microstructure of the samples. The mechanical analysis was evaluated by Vickers microhardness measurements. The structure and microstructure of alloys were sensitive to molybdenum and zirconium concentration, presenting α′, α″ and β phases. Molybdenum proved to have greater β-stabilizer action than zirconium. Microhardness was changed with addition of molybdenum and zirconium, having Ti-15Zr-10Mo (436 ± 2 HV) and Ti-15Mo-10Zr (378 ± 4 HV) the highest values in each system.

Influence of thermal parameters on the dendritic arm spacing and the microhardness of Al-5.5wt.%Sn alloy directionally solidified

As ligas Al-Sn são amplamente utilizados em aplicações tribológicas. Nesse estudo, análises térmica, microestrutural e dureza (HV) foram realizadas ao longo de um lingote da liga Al-5,5%Sn, obtido por solidificação direcional horizontal transitória. Os principais parâmetros analisados incluem a velocidade de deslocamento da isoterma liquidus (V_L) e a taxa de resfriamento (T_R). Esses parâmetros térmicos desempenham um papel fundamental na formação da microestrutura. A microestrutura dendrítica foi caracterizada através dos espaçamentos dentríticos primários (λ₁), os quais foram determinados, experimentalmente, e correlacionados com V_L, e T_R. O comportamento apresentado pela liga Al- 5,5% Sn, durante a solidificação,é semelhante ao de outras ligas de alumínio, isto é, observa-se rede dendrítica mais grosseira com a diminuição da taxa de resfriamento, indicando que a imiscibilidade entre o alumínio e estanho não tem um efeito significativo sobre o relação entre o espaçamento dendrítico primário e taxa de resfriamento. A dependência da microdureza em V_L, T_R e no λ₁ foi também analisada. Verificaram-se menores valores de HV para maiores T_R. Por outro lado, os valores HV aumentam com valores crescentes de λ₁.

Characterization of atmospheric aerosols in the city of So Paulo, Brazil: comparisons between polluted and unpolluted periods

The objective of this study was to determine the size and composition of atmospheric aerosols in the downtown area of the city of So Paulo, Brazil, for a polluted and an unpolluted period. Aerosols were sampled with a portable air sampler (PAS), Micro-Orifice Uniform Deposit Impactor (MOUDI), and Scanning Mobility Particle Sizer. At the study site, air quality is poor, especially during the winter, high concentrations of pollutants being emitted primarily by the light- and heavy-duty vehicle fleet. We analyzed mass, black carbon (BC), Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sn, Zr, and Pb. During the polluted period, diurnal PM(10) was higher than nocturnal PM(10), whereas the inverse was true during the unpolluted period. The FPM was rich in BC, S, and Pb, whereas CPM was rich in Al, Si, Ca, Ti, and Fe. Mass balance was performed by category: ammonium sulfate, sodium chloride, crustal material, BC, and other. The PAS-determined FPM was mainly BC. The MOUDI-determined FPM crustal material explained more mass than did ammonium sulfate and BC during the polluted period, whereas ammonium sulfate had the largest mass during the unpolluted period. Crustal material was the major CPM component, followed by ammonium sulfate and BC. During the unpolluted period, FPM concentrations were lower, whereas those of ammonium sulfate were relatively higher, especially at night, and particle number was inversely proportional to particle size. Aerosol growth was more intense during the polluted period.

Optimization of x-ray spectra in digital mammography through Monte Carlo simulations

In this work, a Monte Carlo code was used to investigate the performance of different x-ray spectra in digital mammography, through a figure of merit (FOM), defined as FOM = CNR2/(D) over bar (g), with CNR being the contrast-to-noise ratio in image and (D) over bar (g) being the average glandular dose. The FOM was studied for breasts with different thicknesses t (2 cm <= t <= 8 cm) and glandular contents (25%, 50% and 75% glandularity). The anode/filter combinations evaluated were those traditionally employed in mammography (Mo/Mo, Mo/Rh, Rh/Rh), and a W anode combined with Al or K-edge filters (Zr, Mo, Rh, Pd, Ag, Cd, Sn), for tube potentials between 22 and 34 kVp. Results show that the W anode combined with K-edge filters provides higher values of FOM for all breast thicknesses investigated. Nevertheless, the most suitable filter and tube potential depend on the breast thickness, and for t >= 6 cm, they also depend on breast glandularity. Particularly for thick and dense breasts, a W anode combined with K-edge filters can greatly improve the digital technique, with the values of FOM up to 200% greater than that obtained with the anode/filter combinations and tube potentials traditionally employed in mammography. For breasts with t < 4 cm, a general good performance was obtained with the W anode combined with 60 mu m of the Mo filter at 24-25 kVp, while 60 mu m of the Pd filter provided a general good performance at 24-26 kVp for t = 4 cm, and at 28-30 and 29-31 kVp for t = 6 and 8 cm, respectively.

Atmospheric corrosion of quaternary bronzes (Cu-Sn-Zn-Pb): laboratory tests (accelerated ageing in wet & dry conditions)and field studies (the Bottego monument in Parma, Italy).

The interactions between outdoor bronzes and the environment, which lead to bronze corrosion, require a better understanding in order to design effective conservation strategies in the Cultural Heritage field. In the present work, investigations on real patinas of the outdoor monument to Vittorio Bottego (Parma, Italy) and laboratory studies on accelerated corrosion testing of inhibited (by silane-based films, with and without ceria nanoparticles) and non-inhibited quaternary bronzes are reported and discussed. In particular, a wet&dry ageing method was used both for testing the efficiency of the inhibitor and for patinating bronze coupons before applying the inhibitor. A wide range of spectroscopic techniques has been used, for characterizing the core metal (SEM+EDS, XRF, AAS), the corroded surfaces (SEM+EDS, portable XRF, micro-Raman, ATR-IR, Py-GC-MS) and the ageing solutions (AAS). The main conclusions were: 1. The investigations on the Bottego monument confirmed the differentiation of the corrosion products as a function of the exposure geometry, already observed in previous works, further highlighting the need to take into account the different surface features when selecting conservation procedures such as the application of inhibitors (i.e. the relative Sn enrichment in unsheltered areas requires inhibitors which effectively interact not only with Cu but also with Sn). 2. The ageing (pre-patination) cycle on coupons was able to reproduce the relative Sn enrichment that actually happens in real patinated surfaces, making the bronze specimens representative of the real support for bronze inhibitors. 3. The non-toxic silane-based inhibitors display a good protective efficiency towards pre-patinated surfaces, differently from other widely used inhibitors such as benzotriazole (BTA) and its derivatives. 4. The 3-mercapto-propyl-trimethoxy-silane (PropS-SH) additivated with CeO2 nanoparticles generally offered a better corrosion protection than PropS-SH.

108 Sn studied with intermediate-energy Coulomb excitation

In dieser Arbeit wurde der instabile, Neutronenarme Kern 108Sn mit Hilfe der Coulomb-Anregung bei intermediaeren Energien in inverser Kinematik studiert. Diese Methode wurde bisher zur Untersuchung der ersten angeregten 2+ Zustaende und deren E2 Zerfallsraten in Kernen mit Kernladungszahl Z< 30 angewendet. 108Sn ist somit der Kern mit der groeßten Kernladungszahl, bei dem diese Studien bisher stattfanden. Das Ziel dieses Experiments war die Messung der unbekannten reduzierten Uebergangswahrscheinlichkeit B(E2,0+ -> 2+). Der B(E2)-Wert von 0.230(57) e2b2 wurde relativ zu dem bekannten Wert des Isotops 112Sn bestimmt. Das Experiment wurde an der GSI Darmstadt mit Hilfe des RISING Detektors und des Fragmentseperators (FRS) durchgefuehrt. Sekundaere Strahlen (108Sn, 112Sn) mit einer Energie von ca. 150 MeV pro Nukleon wurden auf ein 386 mg/cm2 dickes 197Au Target geschossen. Die Projektilfragmente wurden mit Hilfe des Fragmentseparators selektiert und identifiziert. Zur Selektion des Reaktionskanals und zur Bestimmung des Winkels der gestreuten Fragmente wurde das Teilchenteleskop CATE, das sich hinter dem Target befand, verwendet. Gammastrahlung, die in Koinzidenz mit den Projektilrestkernen emittiert wurde, wurde in den Germanium-Cluster Detektoren des RISING Detektors nachgewiesen. Der gemessene B(E2,0+ -> 2+)-Wert von 108Sn ist in Uebereinstimmung mit neueren Schalenmodellrechnungen, die auf realistischen effektiven Wechselwirkungen basieren und im Rahmen eines verallgemeinerten Seniorit¨ats-Schemas erklaert werden.

Grazing incidence pumped Zr x-ray laser for spectroscopy on Li-like ions

X-ray laser fluorescence spectroscopy of the 2s-2p transition in Li-like ions is promising to become a widely applicable tool to provide information on the nuclear charge radii of stable and radioactive isotopes. For performing such experiments at the Experimental Storage Ring ESR, and the future NESR within the FAIR Project, a grazing incidence pumped (GRIP) x-ray laser (XRL) was set up at GSI Darmstadt using PHELIX (Petawatt High Energy Laser for heavy Ions eXperiments). The experiments demonstrated that lasing using the GRIP geometry could be achieved with relatively low pump energy, a prerequisite for higher repetition rate. In the first chapter the need of a plasma XRL is motivated and a short history of the plasma XRL is presented. The distinctive characteristic of the GRIP method is the controlled deposition of the pump laser energy into the desired plasma density region. While up to now the analysis performed were mostly concerned with the plasma density at the turning point of the main pump pulse, in this thesis it is demonstrated that also the energy deposition is significantly modified for the GRIP method, being sensitive in different ways to a large number of parameters. In the second chapter, the theoretical description of the plasma evolution, active medium and XRL emission properties are reviewed. In addition an innovative analysis of the laser absorption in plasma which includes an inverse Bremsstrahlung (IB) correction factor is presented. The third chapter gives an overview of the experimental set-up and diagnostics, providing an analytical formula for the average and instantaneous traveling wave speed generated with a tilted, on-axis spherical mirror, the only focusing system used up to now in GRIP XRL. The fourth chapter describes the experimental optimization and results. The emphasis is on the effect of the incidence angle of the main pump pulse on the absorption in plasma and on output and gain in different lasing lines. This is compared to the theoretical results for two different incidence angles. Significant corrections for the temperature evolution during the main pump pulse due to the incidence angle are demonstrated in comparison to a simple analytical model which does not take into account the pumping geometry. A much better agreement is reached by the model developed in this thesis. An interesting result is also the appearance of a central dip in the spatially resolved keV emission which was observed in the XRL experiments for the first time and correlates well with previous near field imaging and plasma density profile measurements. In the conclusion also an outlook to the generation of shorter wavelength XRL’s is given.

Synthesis and characterization of metal-chalcogenide MQ 2-Nanoparticles (M = Mo, W, Zr; Q = S, O)

Here, we present the adaptation and optimization of (i) the solvothermal and (ii) the metal-organic chemical vapor deposition (MOCVD) approach as simple methods for the high-yield synthesis of MQ2 (M=Mo, W, Zr; Q = O, S) nanoparticles. Extensive characterization was carried out using X-ray diffraction (XRD), scanning and transmission electron micros¬copy (SEM/TEM) combined with energy dispersive X-ray analysis (EDXA), Raman spectroscopy, thermal analyses (DTA/TG), small angle X-ray scattering (SAXS) and BET measurements. After a general introduction to the state of the art, a simple route to nanostructured MoS2 based on the decomposition of the cluster-based precursor (NH4)2Mo3S13∙xH2O under solvothermal conditions (toluene, 653 K) is presented. Solvothermal decomposition results in nanostructured material that is distinct from the material obtained by decomposition of the same precursor in sealed quartz tubes at the same temperature. When carried out in the presence of the surfactant cetyltrimethyl¬ammonium bromide (CTAB), the decomposition product exhibits highly disordered MoS2 lamellae with high surface areas. The synthesis of WS2 onion-like nanoparticles by means of a single-step MOCVD process is discussed. Furthermore, the results of the successful transfer of the two-step MO¬CVD based synthesis of MoQ2 nanoparticles (Q = S, Se), comprising the formation of amorphous precursor particles and followed by the formation of fullerene-like particles in a subsequent annealing step to the W-S system, are presented. Based on a study of the temperature dependence of the reactions a set of conditions for the formation of onion-like structures in a one-step reaction could be derived. The MOCVD approach allows a selective synthesis of open and filled fullerene-like chalcogenide nanoparticles. An in situ heating stage transmission electron microscopy (TEM) study was employed to comparatively investigate the growth mechanism of MoS2 and WS2 nanoparticles obtained from MOCVD upon annealing. Round, mainly amorphous particles in the pristine sample trans¬form to hollow onion-like particles upon annealing. A significant difference between both compounds could be demonstrated in their crystallization conduct. Finally, the results of the in situ hea¬ting experiments are compared to those obtained from an ex situ annealing process under Ar. Eventually, a low temperature synthesis of monodisperse ZrO2 nanoparticles with diameters of ~ 8 nm is introduced. Whereas the solvent could be omitted, the synthesis in an autoclave is crucial for gaining nano-sized (n) ZrO2 by thermal decomposition of Zr(C2O4)2. The n-ZrO2 particles exhibits high specific surface areas (up to 385 m2/g) which make them promising candidates as catalysts and catalyst supports. Co-existence of m- and t-ZrO2 nano-particles of 6-9 nm in diameter, i.e. above the critical particle size of 6 nm, demonstrates that the particle size is not the only factor for stabilization of the t-ZrO2 modification at room temperature. In conclusion, synthesis within an autoclave (with and without solvent) and the MOCVD process could be successfully adapted to the synthesis of MoS2, WS2 and ZrO2 nanoparticles. A comparative in situ heating stage TEM study elucidated the growth mechanism of MoS2 and WS2 fullerene-like particles. As the general processes are similar, a transfer of this synthesis approach to other layered transition metal chalcogenide systems is to be expected. Application of the obtained nanomaterials as lubricants (MoS2, WS2) or as dental filling materials (ZrO2) is currently under investigation.