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No description available.

Amongst treatment technologies, adsorption is rapidly gaining prominence because it can remove metal pollutants at low concentrations, economical, ease of operation, and the adsorbent can be regenerated for reuse. This study therefore, aimed at developing a simple material for selective removal of cesium from wastewater. An agricultural waste material (pine cone) was used as a cheap solid support for transition metal hexacyanoferrate and applied as biosorbents for cesium removal. The preparation and characterization of biosorbent for cesium removal in the presence of alkali metals is reported. The experimental procedure was carried out in three phases; the first phase described the sample preparation. Toluene-ethanol mixtures of different ratios were investigated as surface treatment method for pine cone and the optimum treatment ratio determined by measuring the improvement in surface properties of the pine cone such as bulk density, iodine number, and surface negative charge. The modification of pine cone with iron hexacyanoferrate was examined in the second phase. The preparation of potassium iron(III) hexacyanoferrate (KFeHCF) supported toluene-ethanol modified pine cone powder was studied in order to consider its application for cesium removal from aqueous solution. The biosorbent was designed to incorporate the hexacyanoferrate ligand which is known to have a high affinity for cesium ions in aqueous solution. Fe(III) was loaded onto the toluene-ethanol treated pine cone powder followed by hexacyanoferrate ligand incorporation on the biosorbent producing the potassium iron hexacyanoferrate supported toluene-ethanol treated pine cone. The modified pine cone was characterized by FTIR, XRD and TGA analysis. The influence of solution pH and adsorbent dose were studied. The application of potassium iron hexacyanoferrate for the selective removal of cesium in the presence of sodium and calcium was investigated in the third phase. Batch adsorption kinetic studies were performed to determine the effect of modification on cesium removal. Coefficient of correlation, r2, and Chi-square, χ2, methods were applied in the determination of the best fit kinetic method. Increasing the ratio of toluene in the extractant mixture increased formation of esters and iodine capacity of the material, but reduced carboxylate ions and surface charge. Maximum cesium vi adsorption was observed for the 2:1 toluene-ethanol treated sample. Structural characterization using FTIR, XRD and TGA confirmed the successful modification of KFeHCF pine cone powder. Cesium adsorption experiments indicate that KFeHCF supported toluene-ethanol modified pine was more efficient for cesium removal than the raw pine cone powder. Kinetic modeling of Cs+ adsorption was done using the pseudo-first, pseudo-second order and diffusion chemisorption kinetic models. The pseudo first order kinetics could not accurately predict the experimental data. The kinetics data fitted the pseudo-second order and diffusion-chemisorption models. The chemisorption diffusion model only accurately describes the experimental data after 5 min of contact whereas the pseudo second order describes the experimental data over the range of contact time. The application of the FeHCF modified pine cone for cesium removal from aqueous solution revealed that the FeHCF modified pine was less affected by the presence of competitive cations than the toluene-ethanol treated sample and the raw pine cone sample.

Apresentamos resultados experimentais sobre o comportamento fora de centro do íon de Cu+ em cristais de RbCl, RbBr, RbI, NaI e em cristais mistos de KI +%KCl e KCl +%KI; como também do íon de Ag+ em RbI. Usamos técnicas de absorção ótica no ultra travioleta, corrente termoestimulada (ITC) e dicroísmo induzido por pressão uniaxial. Com estas técnicas, determinamos o comportamento da força do oscilador em dependência com a temperatura, energia de ativação, tempo de relaxação em dependência com a temperatura, momento dos dipolos elétricos, a mudança de configuração do íon de Cu + na reorientação num sistema de multipoço trigonal . puro para um multipoço ortorrómbico no crital misto de KI+1%KCl. Detetamos pela primeira vez a relaxação por ativação térmica de bandas de ITC a temperatura relativamente baixa, como é o caso do íon de Ag+ em RbI que acontece em 24ºK. Ainda, apresentamos alguns resultados sobre o comportamentp do íon de Li + que fica fora de centro no KC1, em cristais de KCl contendo centros U de H- e de D-, usando absorção ótica no infravermelho médio. / Experimental results are given on the off-center behavior of Cu+ ion in RbCl, RbBr, Hbl, NaI and in mixed crystals of KI+%KCl and KCl+%KI, as also on Ag+ in RbI. We use UV optical absorption, ionic thermal current (ITC) and uniaxial stress induced dichroism techniques. It is studied the temperature dependence of the oscillator strength, the relaxation time and the electric dipo1e moment are determined in the above crystals. We observe and discuss the change on the equi1ibrium configuration trigonal of the Cu+ ion in KI to the ortorrhombic in Kl+%KCl mixed crystal. For the first time we detect with the ITC measurements a thermal activated process at low temperature (24ºK), this behaviour occurs in RbI:Ag+. Using mid-infrared absorption measurements, we give several results and discussions on the U centers (either H- or D-) perturbed by Li+ ion in KCl crystals.

O uso do biodiesel está em expansão no mercado mundial. A presença de metais alcalinos é um dos parâmetros de qualidade que mais se destaca devido aos prejuízos que pode causar ao automóvel. Neste trabalho propôs-se um método alternativo para determinar íon sódio usando um sensor eletroquímico baseado em eletrodo quimicamente modificado (EQM) com filme de octafenilciclotetrasiloxano (OFCTS), o qual possui estrutura molecular sugestiva para uma coordenação com Na+. A caracterização do sensor foi realizada por Espectroscopia de Infravermelho com Transformada de Fourier (FT-IR) e Difração de Raios X (DRX). A interação metal:ligante foi estuda por cálculos teóricos, Espectrofotometria UV-Vis, Espectroscopia de Impedância Eletroquímica (EIE) e Voltametria Cíclica (VC). A imobilização do OFCTS no eletrodo de carbono vítreo foi alcançada por adsorção usando a técnica drop coating. O par redox [Ru(NH 3)5 Cl] 2+/3+foi empregado como íon sonda e a corrente de pico (Ip) foi monitorada por voltametria de pulso diferencial com varredura anódica. Adições sucessivas de Na+ à célula eletroquímica causaram a diminuição da Ip do íon sonda, devido à interação do íon sódio com o ligante imobilizado no eletrodo e consequente repulsão com o íon sonda. Empregando este efeito, a concentração de íons sódio pode ser indiretamente medida. Após a otimização dos principais parâmetros da eletroanálise, a curva analítica foi construída através da relação entre diferença de Ip (δIp) do [Ru(NH 3) 5Cl]2+/3+e a quantidade de íons sódio adicionada, obtendo um coeficiente de correlação (r) de 0,998, LD e LQ iguais a 0,38 mg kg -1 e 1,29 mg kg-1 , respectivamente. As amostras de biodiesel foram preparadas por digestão ácida por via úmida com radiação de micro-ondas. As recuperações foram obtidas e os percentuais para a fortificação foi biodiesel 105% e para água mineral foi 81%. O método alternativo foi aplicado para amostra real e detectou 4,1 mg Kg-1 de sódio em biodiesel. / The use of biodiesel is expanding in the world market. The presence of alkali metals is one of its quality parameters that stand out, due to the damage that they can cause to vehicles. This study aimed to propose an alternative method to determine sodium ions using an electrochemical sensor based on chemically modified electrode (CME) with octaphenylcyclotetrasiloxane (OFCTS), which has suggestive molecular structure for coordination with Na+ ion. The characterization of the sensor was carried out by Fourier Transform Infrared Spectroscopy (FT-IR) and X-Ray Diffraction (XRD). The metal:ligand interaction was studied by theoretical calculations, UV-Visible Spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV). Immobilization of OPCTS on glassy carbon electrode was achieved by adsorption through drop coating technique. The [Ru(NH 3) 5Cl]2+/3+e redox couple was used as ion probe, and its peak current (Ip) was monitored by stripping anodic stripping differential pulse voltammetry . Successive additions of Na+ to the electrochemical cell promote the Ip decrease of the ion probe, due to interaction between the sodium ion and the immobilized ligand on the electrode and the subsequent repulsion with the ion probe. Using this effect, the sodium ions concentration could be indirectly measured. After the main parameters optimization of the electroanalysis, the analytical curve was constructed by plotting the Ip difference (δIp) of [Ru(NH 3) 5Cl]2+/3+e against the amount of sodium ions added, obtaining a coefficient of correlation (r 2) of 0.99 and LOD and LOQ equal to 0,38 and 1,29 mg Kg-1, respectively. The biodiesel samples were pretreated by microwave assisted acid digestion. Recoveries were obtained and the percentages for the fortification for biodiesel was 105,5% and for mineral water was 81%. The alternative method was applied for real sample and detected 4 mg Kg -1 of the sodium in biodiesel.

Átomos alcalinos são boas sondas para compreender as propriedades do He líquido. Considerável atenção experimental tem sido empregada para analisar as mudanças da posição e da largura da linha do espectro de absorção de átomos alcalinos imersos em um ambiente de He líquido. No lado teórico, vários estudos têm usado modelos simplificados como o modelo de bolhas e o modelo de agregado. Considerações de modelos mais realista agora são oportunas e relevantes. Neste trabalho, nós usamos a combinação da simulação de Monte Carlo (MC) e cálculos ab-initio de mecânica quântica (MQ). As configurações do líquido foram geradas para cálculos posteriores de MQ.Umimportante aspecto é a complexa interação interatômica do par He-He. Usando potenciais parametrizados, as simulações clássicas de MC foram efetuadas para sistemas alcalinos (Na, Rb, Cs e Na2) em He líquido e as condições foram T = 3 K e p = 1 atm. Estruturas estatisticamente descorrelacionadas formadas por um elemento alcalino central, envolvido pela primeira camada de solvatação completa, são amostradas e submetidas em um cálculo do espectro com DFT dependente do tempo usando diferentes funcionais híbridos e conjuntos de bases. Usando os funcionais PBE1PBE e O3LYP com conjuntos de bases extensos obtemos o deslocamento espectral em excelente concordância com os resultados experimentais para os sistemas de um único átomo alcalino. Para comparação, também usamos um modelo de agregado com 14 átomos de He em volta do átomo alcalino obtendo excelentes resultados também. O raio do modelo de agregado convergiu para perto do máximo da primeira camada de solvatação da função de distribuição radial. Um ponto adicional a ser considerado é o cálculo da largura da linha obtido com a simulação em He líquido que é discutida neste trabalho. Para o átomo de Rb, a energia de excitação em He líquido é em torno de -18,9 nm. Com a simulação em ambiente de He líquido obtivemos os melhores resultados entre -16,3 nm e -23,3 nm. O valor do deslocamento espectral usando o modelo de agregado ficou entre os -17,3 nm e - 22,3 nm. Os dois modelos apresentam o mesmo raio da bolha, por volta de 6-7Å. Para outros sistemas, como Na e Cs, encontramos a mesma convergência entre o modelo de agregado, a simulação do He líquido e os resultados experimentais. Para o sistema contendo Na2, os valores obtidos ficaram em boa concordância com os valores experimentais. / Alkali atoms are good probes for the understanding of liquid He properties. As such considerable experimental attention has been devoted to the analysis of the changes of line position and widths of the absorption spectra of alkali atoms in liquid He environment. On the theoretical side, several studies have used simplified models such as bubble and cluster models. Considerations of more realistic models are now timely and relevant. In this work, we use a combination of Monte Carlo (MC) simulation and ab initio quantum mechanical (QM) calculations. Liquid configurations are generated for subsequent QM calculations. One important aspect is the consideration of the complex interatomic interaction of the He-He pair. Using parametrized potentials, classical MC simulations are made for the alkali systems (Na, Rb, Cs and Na2) in liquid He. The conditions were T=3K and p=1 atm. Statistically uncorrelated configurations composed of a central alkaline element, surrounded by the full first solvation shell, are sampled and submitted to time-dependent DFT calculations of the spectrum using dierent hybrids functionals and dierents basis sets. Using the PBE1PBE and O3LYP functionals with large basis sets we obtained a spectral shift in excellent agreement with experiment for the systems of single alkaline atom. For comparison, we also used a cluster model and obtained 14 He atoms around the alkali atom with excellent results too. The radius of the cluster model converged to a value close to the maximum of the first solvation shell in radial distribution function. An additional point considered is the calculation of the spectral line width using the liquid simulation also discussed in this work. For Rb atom, the excitation energy in liquid He is about -18.9 nm. With the liquid He environment simulation we obtained the best results between -16.3 nm and -23.3 nm. The values of the spectral shift using the cluster model were between -17.3 nm and 22.3 nm. The two models show the same bubble radius, about 6-7Å. For the others system, like Na and Cs, we found the same convergence between the cluster model, the simulation of the He liquid and the experimental results. For Na2, the values obtained were in good agreement to the experimental values.

Os modos vibracionais localizados dos pares H-H-, D-D- e H-D- em KCl, KBr, KI, RbCl e NaCl foram estudados para diversas configurações. As frequências dos modos infravermelho ativos determinados experimentalmente mostram boa concordância com o modelo de dois osciladores harmônicos acoplados. A largura de linha para os diferentes modos nos cristais examinados é discutida. A dependência com a temperatura da largura de linha para os modos transversais T1 e T2 no sistema KCl+ H- H-, indica que o alargamento das mesmas é devida ao \"mecanismo de decomposição\", no qual dois fônons são criados. Estes fônons são devidos ao decaimento do modo localizado em fase num fônon acústico da rede e num fônon localizado fora de fase. Propriedades gerais, como a lei de Ivey e diversas outras particularidades dos halogenetos alcalinos estudados são apresentadas / The localized vibrational modes of H-H-, D-D- and H-D- in KCl, KBr, KI, RbCl and NaCl were studied for different pair configurations. The measured frequencies of the infrared active modes were found to be in good agreement with a model of two coupled harmonic oscillators. The line width for different modes in the salts studied is discussed. The temperature dependence for the transversal modes T1 and T2 of the line width for the H- H- pairs in KCl indicates that the broadening of these lines is due to the \"decomposition mechanism\", that generates two phonons. The generated phonons due to the decay of the localized phonon that corresponds to the out of phase vibration of the H- H- pair. The general properties, as the Ivey law and several particulars of the properties in the alkali-halides studied are presented

Motivados por trabalhos anteriores que analisaram diferentes comportamentos entre cristais e filmes policristalinos, relacionados com a cristalinidade e a concentração de impurezas, neste trabalho investigamos métodos de obtenção e processamento de filmes de haletos alcalinos dopados. Durante este trabalho foi montado um sistema de evaporação que disponibilizou a utilização de duas fontes de evaporação para a produção de amostras: resistiva e via feixe de elétrons. Apresentamos uma comparação entre resultados de caracterizações dos filmes produzidos e de monocristais existentes na literatura. A fim de se obter filmes dopados com impurezas mono e divalente e, também, duplamente dopados, alguns métodos alternativos de processamento foram investigados. A partir da comparação entre os sistemas KCl:(In +, Tl+ e Cu+) determinamos a dependência da cristalinidade em função do tamanho do íon dopante. O efeito da temperatura do substrato durante a evaporação foi investigado para o sistema KCl:Tl+, e comparado com resultados obtidos em filmes submetidos a tratamentos térmicos. Para a obtenção de filmes do sistema KCl:Yb2+:CN-, a preparação dos materiais precursores é um aspecto muito importante a ser considerado, a fim de se reproduzir nos filmes propriedades similares às dos monocristais. Nesse sentido, para evaporação foram utilizados o próprio cristal e pastilhas dos sais precursores obtidas a partir de técnicas de processamento cerâmico. A caracterização óptica dos filmes foi feita através de espectroscopia de absorção óptica e luminescência. A morfologia foi observada através de microscopia eletrônica de varredura e de força atômica, e a estrutura determinada por técnica de difração de raios X / The present work has been motivated by previous research on doped alkali halides films, that had been compared with single crystals, yielding different features, wich were related to crystallinity and impurity concentration. Preparation and processing techniques of doped alkali halides polycrystalline films have been investigated in this work. Two different evaporation sources have been used for samples production: resistive and via electron beam gun. Main results presented here are used to compare single crystals and films. In order to prepare single and double doped films, we have also tried several processing methods. From investigation of KCl:Tl+ system we have determined crystallinity dependency with impurity ion size. The KCl:Tl+ system has been used to verify the effect of substract temperature during evaporation. Results have been compared with films submited to thermal annealing. To obtain double doped KCI:Yb2+ :CN- films, we were very careful with preparation of precursor materials, since we intended to reproduce single crystals physical properties. Then, we have used single crystal itself for evaporation, besides pressed power pieces from precursor salts, obtained from ceramics processing technique. Optical absorption and photoluminescence have been carried out to perform optical characterization of evaporated films. Morphology has been observed by atomic force microscopy and scanning electron microscopy, and film structure has been observed by X-ray diffraction technique

The American Society of Civil Engineers’ (ASCE’s) “2013 Report Card for America’s Infrastructure” estimated that “32% of America’s major roads are in poor or mediocre condition.” An estimated $100 billion dollars are needed to maintain that condition, and an additional $79 billion is needed to improve the quality of American roadways to an acceptable level. In many regions around the US, the service lives of concrete pavements are limited by the damage caused by freezing and thawing of pore solution inside the pavements. Alkali-activated slags (AAS) are produced from ground granulated blast furnace slag (GGBFS), a byproduct of iron production, and exhibit cementitious properties. AAS concretes have been shown to have improved corrosion and freeze/thaw resistance compared to traditional cementbased concretes. A Guarded Longitudinal Comparative Calorimeter (GLCC) was used to determine when the freezing and thawing of internal water occurs in three AAS mortars using solutions of NaOH, Na2CO3, or waterglass compared to a control Ordinary Portland Cement (OPC) mortar. AAS mortars using NaOH and Na2CO3 showed comparable thermal properties to the OPC mortar using the GLCC, and the AAS mortar using waterglass was shown to have higher heat capacity compared to the other AAS mixes. The compressive strengths varied by the alkaline solution used, with AAS with Na2CO3 showing inferior compressive strength to OPC, AAS with NaOH showing similar compressive strength to OPC, and AAS with waterglass showing superior compressive strength to OPC, but poor workability. A computer model of the GLCC testing procedure was created and showed good agreement with the experimental data. The GLCC model can be modified to approximate the results of the GLCC using a wider range of materials and internal solutions, like PCMs.

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