Development and evaluation of a pollution prevention technology for surface cleaning and decontamination : cooperative research and development agreement with Cold Jet, Inc.

Mode of access: Internet.

Coḿo reducir los peligros del plomo al remodelar su casa.

Mode of access: Internet.

Electromechanical properties of engineered lead free potassium sodium niobate based materials

K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

Fe valence fluctuations and magnetoelastic coupling in Pb-based multiferroics perovskites

Lead-based multiferroics perovskites with nominal compositions Pb(Fe1/2Nb1/2)O3 and Pb(Fe2/3W1/3)O3 were synthesized following a two-stage method. Magnetic proprieties were investigated and correlated to anelastic proprieties, measured by the conventional pulse-echo method. The discussions are focused in the region around 250 K, where magnetoelectroelastic instabilities have been observed. X-ray absorption nearedge structure (XANES) study further indicates that the edge position varies with temperature revealing a fluctuation on the valence of iron ions with the temperature, which can be related to a variation in anelastic and magnetic proprieties.

Fighting rust with sublimed blue lead; an assembly of facts concerning the properties and uses of sublimed blue lead.

Mode of access: Internet.

Environmental lead contamination in Miami inner-city area

The purpose of the study was to evaluate the magnitude of environmental lead contamination in the downtown area of Miami. Lead inspections took place at 121 homes in Little Haiti and Liberty City and involved the collection ofrepresentative samples from floors, window wells, tap water, soil and air. Community health workers (CHWs) trained in interview and safety techniques went from door to door to enlist participation. On-site investigations were tailored to areas most utilized by children underthe age of6 years. The presence of lead-containing paint was also investigated in situ via X-ray fluorescence (XRF) analysis. Results: Of the sampling areas, the window wells area had the most abundant occurrence of lead. On analysis, 24% of sites returned window well samples with lead levels above Department of Housing and Urban Development (HUD) guidelines. Of the soil samples, the playgrounds around the house had the highest concentration of lead. Soil sampling demonstrated that 27.5% of sites returned samples with lead levels (400 to 1600 ppm) inexcess of HUD/Environmental Protection Agency (EPA) standards. Positive XRF readings in one or more components were returned by 18% of sites. Conclusions: More than half of the houses in these two neighborhoods exhibited unacceptably high levels of lead dust and soil in areas where children live and play. Limitations of this study did not allow the assessment of how many children in this area are affected. A more comprehensive study including other areas of Miami-Dade County with older housing stock is recommended.

Procuring Sydney’s Olympic Stadium : a world class event?

This paper describes and analyses the procurement processes employed in delivering the Sydney Olympic Stadium – arguably the most significant stadia project in the region today. This current high profile project is discussed in terms of a case study into the procurement processes used. Interviews, personal site visits and questionnaires were used to obtain information on the procurement processes used and comments on their application to the project. The alternative procurement process used on this project—Design and Construction within a Build, Own, Operate and Transfer (BOOT) project—is likely to impact on the construction industry as a whole. Already other projects and sectors are following this lead. Based on a series of on-site interviews and questionnaires, a series of benefits and drawbacks to this procurement strategy are provided.The Olympic Stadium project has also been further analysed during construction through a Degree of Interaction framework to determine anticipated project success. This analysis investigates project interaction and user satisfaction to provide a comparable rating. A series of questionnaires were used to collect data to calculate the Degree of Interaction and User Satisfaction ratings.

Incentive compatible mechanisms for group ticket allocation in software maintenance services

A customer reported problem (or Trouble Ticket) in software maintenance is typically solved by one or more maintenance engineers. The decision of allocating the ticket to one or more engineers is generally taken by the lead, based on customer delivery deadlines and a guided complexity assessment from each maintenance engineer. The key challenge in such a scenario is two folds, un-truthful (hiked up) elicitation of ticket complexity by each engineer to the lead and the decision of allocating the ticket to a group of engineers who will solve the ticket with in customer deadline. The decision of allocation should ensure Individual and Coalitional Rationality along with Coalitional Stability. In this paper we use game theory to examine the issue of truthful elicitation of ticket complexities by engineers for solving ticket as a group given a specific customer delivery deadline. We formulate this problem as strategic form game and propose two mechanisms, (1) Division of Labor (DOL) and (2) Extended Second Price (ESP). In the proposed mechanisms we show that truth telling by each engineer constitutes a Dominant Strategy Nash Equilibrium of the underlying game. Also we analyze the existence of Individual Rationality (IR) and Coalitional Rationality (CR) properties to motivate voluntary and group participation. We use Core, solution concept from co-operative game theory to analyze the stability of the proposed group based on the allocation and payments.

Do confronto à conciliação : debates presidenciais na TV como eventos persuasivos

Este estudo faz uma análise dos debates presidenciais na televisão como eventos persuasivos de campanha. O objetivo foi contribuir para a compreensão não só do papel dessa fonte de informação política no contexto brasileiro, mas discutir também de maneira sistemática os seus possíveis efeitos. Os debates na TV são uma variável comunicacional de curto prazo dos processos eleitorais. Eles oferecem estímulos comunicacionais que são disseminados no ambiente da campanha, seja por quem o assiste diretamente, seja por quem fica sabendo desses eventos e dos desempenhos dos candidatos através de outros dispositivos, como a imprensa e o Horário da Propaganda Gratuita Eleitoral (HPGE). Como apenas informação não basta para explicar mudanças de opinião, focamos o estudo em dois eixos principais. O primeiro deles na identificação e no mapeamento das estratégias persuasivas adotadas pelos candidatos, porque eles são instados a confrontar seus adversários, num evento ao vivo, e por meio do qual os eleitores podem avaliar não só o seu posicionamento político, como a maneira que se apresentam. Está presente, neste caso, um impacto sobre a atitude dos eleitores com relação aos competidores. Os principais resultados indicam haver um padrão no objetivo das mensagens, prevalecendo, no agregado, o ataque entre os candidatos da oposição, e a aclamação entre os candidatos da situação. O posicionamento do candidato, bem como o conteúdo político das mensagens apresentaram resultados significativos para um possível efeito sobre a atitude dos eleitores. No estudo, propomos ainda a análise dos enquadramentos adotados pelos competidores, cuja função é estabelecer um quadro de referência para a audiência. Esta variável, que procura levar em conta aspectos da comunicação verbal e nãoverbal, também apresentou resultados significativos. No segundo eixo analítico, tratamos dos efeitos agregados desses acontecimentos de campanha. Foram analisados os debates de 2002, quando prevalecia um clima de opinião favorável à oposição, e 2010, quando o clima é favorável à situação. Com relação ao impacto dos debates no ambiente informacional, os dados sugerem que, em 2002, a atuação de Luiz Inácio Lula da Silva (PT), candidato da oposição, levou a uma ampliação da cobertura jornalística positiva sobre o candidato; enquanto houve um declínio dessa cobertura para José Serra (PSDB), candidato da situação. Em 2010, na cobertura da imprensa após os debates, tanto a candidata da situação, Dilma Rousseff (PT), quanto o da oposição, José Serra, apresentaram equilíbrio. O impacto no ambiente informacional da campanha foi acompanhado de um aumento da intenção de voto agregada para os candidatos que lideravam as pesquisas e que representavam a mudança em 2002, no caso Lula, ou a continuidade em 2010, no caso Dilma. Nas duas eleições, portanto, os debates na TV no Brasil indicaram ser eventos persuasivos importantes, apesar de terem um papel menos central como dispositivo de informação eleitoral e de não levarem à troca de posição entre os competidores nas pesquisas opinião. Mas eles contribuem, ao menos indiretamente, para consolidar e ampliar intenções de voto dos primeiros colocados a partir de uma percepção positiva disseminada sobre os seus desempenhos.

Thermotropic phase boundaries in classic ferroelectrics

High-performance piezoelectrics are lead-based solid solutions that exhibit a so-called morphotropic phase boundary, which separates two competing phases as a function of chemical composition; as a consequence, an intermediate low-symmetry phase with a strong piezoelectric effect arises. In search for environmentally sustainable lead-free alternatives that exhibit analogous characteristics, we use a network of competing domains to create similar conditions across thermal inter-ferroelectric transitions in simple, lead-free ferroelectrics such as BaTiO 3 and KNbO 3. Here we report the experimental observation of thermotropic phase boundaries in these classic ferroelectrics, through direct imaging of low-symmetry intermediate phases that exhibit large enhancements in the existing nonlinear optical and piezoelectric property coefficients. Furthermore, the symmetry lowering in these phases allows for new property coefficients that exceed all the existing coefficients in both parent phases. Discovering the thermotropic nature of thermal phase transitions in simple ferroelectrics thus presents unique opportunities for the design of 'green' high-performance materials.

Spectral design of temperature-invariant narrow bandpass filters for the mid-infrared

The ability of narrow bandpass filters to discriminate wavelengths between closely-separated gas absorption lines is crucial in many areas of infrared spectroscopy. As improvements to the sensitivity of infrared detectors enables operation in uncontrolled high-temperature environments, this imposes demands on the explicit bandpass design to provide temperature-invariant behavior. The unique negative temperature coefficient (dn/dT<0) of Lead-based (Pb) salts, in combination with dielectric materials enable bandpass filters with exclusive immunity to shifts in wavelength with temperature. This paper presents the results of an investigation into the interdependence between multilayer bandpass design and optical materials together with a review on invariance at elevated temperatures.

Controlling ivy attachment to wall surfaces by applying paints, metal meshes and sheets

Growing ivy around buildings has benefits. However, ivy potentially damages buildings which limit its use. Options for preventing ivy attachment were investigated to provide ivy management alternatives. Indoor and outdoor experiments were conducted, where metals (Cu, Zn) and anti-graffiti paints were applied to model wall panels. Metal treatments, in both indoor and outdoor experiments, fully prevented ivy attachment. For Hedera helix, silane-based anti-graffiti paint prevented attachment in the laboratory and required under half the peak detachment force necessary to detach the control in the outdoor experiment. In conclusion, metals and silane-based paint are management possibilities for ivy attachment around buildings.

Substituição de estabilizantes a base de chumbo pelo de cálcio-zinco no processo produtivo de tubos de PVC rígido

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)