Dissertations / Theses on the topic 'Metals'

Orientadores: Antonio José Gomez Cobo, Antonio Guerrero Ruiz
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Alguns compostos organoclorados são motivo de grande preocupação, em razão da elevada toxicidade e persistência, tanto no meio ambiente quanto em organismos vivos. Dentre tais compostos, encontra-se o pentaclorofenol, utilizado para a conservação de madeira e na proteção de lavouras. Uma das tecnologias mais promissoras para o tratamento dessa classe de compostos tóxicos é a hidrodescloração catalítica, através da qual é possível recuperar a matéria-prima utilizada na síntese do contaminante. Embora diferentes catalisadores possam ser utilizados nesta reação, destacam-se os sólidos à base de Pd e Ru, notadamente devido à maior atividade catalítica. No entanto, os elevados preços destes metais nobres podem aumentar significativamente os custos do processo. Nesse contexto, o objetivo do presente trabalho é estudar os efeitos da presença dos metais básicos Fe e Ni em catalisadores à base de Pd e Ru, destinados à hidrodescloração do pentaclorofenol em fase líquida. Para tanto, catalisadores monometálicos e bimetálicos, suportados em alumina (Al2O3) ou titânia (TiO2), foram preparados a partir dos precursores clorados, através do método de co-impregnação a seco. Os sólidos obtidos foram caracterizados por meio das técnicas de adsorção de N2 (método BET), microscopia eletrônica de varredura com espectrometria de energia dispersiva de raios-X (MEV-EDX), espectroscopia fotoeletrônica de raios-X (XPS), redução à temperatura programada (TPR) e microscopia eletrônica de transmissão (MET). A hidrodescloração do pentaclorofenol foi conduzida num reator Parr® do tipo "slurry", à temperatura de 383 K e sob pressão de H2 de 0,5 MPa. Na reação de interesse, a adição de Ni ao catalisador de Ru/TiO2 diminui a atividade catalítica, porém mantém a elevada seletividade de cicloexanol, possibilitando, portanto, uma diminuição do custo do catalisador, sem perda de seletividade. Já para o catalisador de Pd/TiO2, a presença de Ni também diminui a atividade catalítica, assim como observado no caso do catalisador de Ru/TiO2, mas verifica-se uma diminuição da seletividade de fenol. Por sua vez, a adição de Fe ao catalisador de Pd/TiO2 tem pouca influência sobre a atividade e a seletividade, possibilitando, assim, uma significativa diminuição do custo do catalisador, sem prejuízo do desempenho catalítico. Os comportamentos catalíticos observados são analisados e interpretados à luz dos resultados obtidos através das caracterizações dos sólidos, assim como das informações disponíveis na literatura
Abstract: Some organic chlorine compounds are of great concern, because of high toxicity and persistence, both the environment and in living organisms. Among these compounds, is the pentachlorophenol, which is used to Wood conservation and for the protection of crops. A very promising technology to treating this class of toxic compounds is the catalytic hydrodechlorination, through which it is possible the recovery of raw material used in the synthesis of the contaminant. Although various catalysts may be used in this reaction, we highlight the solids Pd and Ru, mainly due to higher catalytic activity. However, the high prices of these noble etals can increase significantly the process costs. In this context, the objective of this work is to study the effects of base metals addition, Fe and Ni, in the catalysts based on Pd and Ru, for the pentachlorophenol hydrodechlorination in liquid phase. For this, monometallic and bimetallic catalysts, supported in alumina (Al2O3) or titanium oxide (TiO2), were prepared from chlorinated precursors by the incipient impregnation method. The obtained solids were characterized by techniques of N2 adsorption (BET method), scanning electronic microscopy with X-ray spectrometry analysis (EDX), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction (TPR) and transmission electronic microscopy. The pentachlorophenol hydrodechlorination was carried out in a "slurry" Parr® reactor, at the temperature of 373 K under the hydrogen pressure of 0,5 MPa. In the interest reaction, the addition of Ni to the Ru/TiO2 catalysts reduces the catalytic activity, but the high cyclohexanol selectivity is maintained, enabling thus, decrease the catalyst cost, without loss of selectivity. To the Pd/TiO2 catalyst, the i presence reduce the catalytic activity, like to the observed to the Ru/TiO2 case, but is verified the decreasing of phenol selectivity. In turn, the Fe addition to the Pd/TiO2 catalyst has little influence on the activity and selectivity, leading thus to a significant decrease in the catalyst cost, without prejudice to the catalytic performance. The observed catalytic behaviors are analyzed and interpreted based in the results obtained through the characterization of solids, as well as information available in the literature
Doutorado
Sistemas de Processos Quimicos e Informatica
Doutor em Engenharia Química

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1998.
Includes bibliographical references (p. 156-162).
The work covers transformation superplasticity of metals, alloys and metal matrix composites. Fundamental studies of transformation superplasticity in unreinforced metals, which either deform plastically or by creep, form the basis of further investigations in metal matrix composites. Experiments and analytical modeling are complemented by numerical analysis. The transformation superplastic behavior is related to microstructure and chemical composition. Based on an existing linear theory, a non-linear model is developed and applied to the experimental data. Numerical methods are used to model the stress-, strain and temperature evolution during the phase transformation. The results are in good agreement with the experiment and analytical predictions. First, transformation superplasticity of iron and iron-TiC composites is demonstrated with strains of 450% and 230% respectively. The reduction of the transformation superplasticity in the composites is attributed to the dissolution of TiC in iron and effect which is shown for iron-carbon alloys. Effects of transient primary creep, ratchetting and partial transformation through the ferrite-austenite phase field are examined. Second, transformation superplasticity of zirconium is demonstrated for the first time with a strain of 270% without fracture. Partial transformation resulting from high cycle frequencies is analyzed and related to material properties and cycle characteristics. Finally, nickel aluminide with unstabilized zirconia particulates shows significant higher strain rates upon thermal cycling as compared to the unreinforced matrix. Although, the fracture strain of 23% is below the superplastic limit, the composite shows a high strain rate sensitivity of m = 0.71, which is a necessary characteristic of transformation superplasticity.
by Peter Zwigl.
Ph.D.

Orientador: Roberto Alves Oliveira
Coorientador: Allynson Takehiro Fujita
Banca: Mariana Carina Frigieri
Banca: Luciano dos Santos Rodrigues
Resumo: Reatores contínuos com leito de lodo biológico anaeróbio, in natura e seco em estufa, foram utilizados para a remoção de metais (Cu+2, Mn+2 e Zn+2) em solução aquosa. Com o lodo in natura avaliou-se o efeito conjunto da bioacumulação e biossorção; e com o lodo seco em estufa o efeito exclusivo da biossorção. Foram utilizadas baixas concentrações de Cu+2, Mn+2 e Zn+2 (0,01 a 5,00 mg L-1), tendo em vista que para a ocorrência de bioacumulação devem ser mantidas condições não tóxicas para os micro-organismos. Portanto, os resultados poderão ser aplicados para o pós-tratamento de efluentes com concentrações remanescentes desses metais, que necessitem de polimento para a disposição final, atendendo aos limites legais de qualidade de água do corpo receptor. Os lodos utilizados foram coletados de reatores anaeróbios horizontal (RAH) e de fluxo ascendente com manta de lodo (UASB) utilizados no tratamento de águas residuárias de suinocultura. A temperatura foi controlada a 20°C em todos os ensaios. Foram avaliadas vazões de 5, 10 e 15 mL min-1, valores de pH 4,0 e 6,0 e concentrações de 0,01, 0,5 e 1,0 mg L-1 de Cu2+ e Mn2+, e de 0,05; 2,5 e 5,0 mg L-1 de Zn2+. O pH ótimo para a remoção de Mn2+ e Zn2+ foi 4,0 e para o Cu2+ não foi verificada diferença. A maior eficiência foi encontrada quando utilizou-se os menores valores de concentração e fluxo para os três biossorventes avaliados. Foi verificado que os valores de concentração de metais utilizados demonstraram não serem tóxicos para... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: Continuous reactors with anaerobic biological sludge bed, in nature and dry in an oven, were used for removal of metals (Cu+2, Mn+2 and Zn+2 ) in aqueous solution. With the sludge in natura it was evaluated the combined effect of bioaccumulation and biosorption; and the dry sludge in greenhouse sole effect of biosorption. It was used lower concentrations of Cu+2, Mn+2 and Zn+2 (0.01 to 5.00 mg L -1 ), considering that for bioaccumulation occurring should be kept non-toxic conditions for the micro-organisms. Therefore, the results can be applied to the posttreatment of effluents with remaining concentrations of these metals, which require polishing to final disposal, meeting the legal limits of quality of the receiving water body. The used sludges were collected from horizontal anaerobic reactors (RAH) and ascendant upflow sludge blanket (UASB) used in the treatment of swine wastewater. The temperature was controlled at 20°C in all tests. It was analyzed outputs of 5, 10 and 15 ml min-1, pH values 4.0 and 6.0 and concentrations of 0.01, 0.5 and 1.0 mg L- 1 Cu+2 and Mn+2, and 0.05; 2.5 and 5.0 mg L -1 Zn+2 . The optimum pH for the removal of Mn+2 and Zn+2 was 4.0 and the Cu+2 it was not verified difference. The highest efficiency was found when it was used the lowest values of concentration and flux for all three reviews biosorbents. It has been found that the metals concentration values used proved not to be toxic to cells of microorganisms present in the sludge in nature,... (Complete abstract click electronic access below)
Mestre

Predmet izučavanja ove disertacije, osim poređenja različitih metoda procene rizika na osnovu karakterizacije kvaliteta sedimenta vodotokova Vojvodine, bilo je i ispitivanje mogućnosti imobilizacije teških metalau sedimentu primenom različitih remedijacionih tehnika kao i određivanje njihove efikasnosti (npr. solidifikacija/stabilizacija silikatnim materijalima, portland cementom, kalcijum-oksidom itd.) u zavisnosti od brojnih faktora. Osim pseudo-ukupnog sadržaja metala određene su i specifičnije frakcije metala sa posebnimosvrtom na određivanje potencijalno biodostupnih frakcija.Rezultati su ukazali da je naosnovu holandskih preporuka sediment pojedinih vodotokova Vojvodine (Begej, DTD-kanal,Nadela, Sava-Šabac) zagađen metalima (klasa 4) i da je neohodno izmuljivanje i remedijacija. Prema USEPA i kanadskim preporukama, neki uzorci su potencijalno toksični, ali nije zabeležena akutna toksičnost za test vrste u pornoj vodi. Za neke uzorke, i pored visoke pseudo-ukupne koncentracije (klasa 4), nije potvrđena potencijalna toksičnost na osnovu odnosa kiselog volatilnog sulfida i simultano ekstrahovanih metala. Dok se ne primene skuplje metode remedijacije i tretmana sedimenta, najbolje rešenje je izolovano skladištenje na specijalnim  deponijama. Naredni koraci bi trebali da budu usresređeni na kontrolu i sprečavanje zagađenja kako bi se obezbedilo da revitalizacija ovih vodotoka ima trajni pozitivan uticaj na životnu sredinu i nesmetanu i bezbednu plovidbu, kao i na primenu određenih remedijacionih metoda. Poređenje rezultata koji su dobijeni različitim procenama kvaliteta sedimenta pokazalo je da ponekad nije dovoljan jedan pristup i da je potrebno je uključiti metode procene biodostupnosti, biotestove i aspekt radioaktivnosti. U uzorku sedimenta koji je korišćen za ispitivanje efikasnosti remedijacionih tretmana, pokazano je da cink, nikal i olovo imaju visok rizik po okolinu, jer seprocenat metala u izmenljivoj i karbonatnoj fazi kretao od 40.1 do 45.2%. Cr i Cd imaju umeren rizik, dok je bakar prisutan u ovim frakcijama u koncentraciji koja predviđa nizak rizik (5.3%). Ovo je u skladu i sa rezultatima analize porne vode i simultano ekstrahovanih metala i kiselog volatilnog sulfida.Istraživanje prikazano u radu je dalo odgovor na pitanje da li remedijacija može uspešno da ukloni zagađenje, u smislu imobilizacije metala u stanje kada oni više neće biti opasnost po okolinu. Svi primenjeni tretmani doveli su dosmanjenja procenta kumulativno izluženih metala iz S/S smeša, ali nijedna smeša tretiranog sedimenta i ispitivanih imobilizacionih agenasa ne pripada grupi inertnog otpada ukoliko se kumulativne izlužene koncentracije metala porede sa koncentracijama koje za otpad propisuje Evropska Unija (2003/33/EC). Ukoliko nam je cilj dobijanje nehazardnog otpada onda moramo primeniti u tretmanu sedimenta kontaminiranog metalima najmanje 30% imobilizaconih agenasa (cementa, kalcijum-oksida). Najveća efikasnost u imobilizaciji metala postignuta je korišćenjem cementa i kalcijum-oksida u smeši (30% cementa i 10% kalcijum-oksida) i primenom termičkog tretmana na višoj temperaturi (1100⁰C) sa glinom (20% gline) što je zaključeno na osnovu koeficijenata difuzije i indeksa izlužljivosti. Dominantan mehanizam izluživanjametala iz ovih smeša je difuzija.
This work is concerned with the comparison of the different methods of metal risk assessment in sediments based on examination of the qualityof water courses in Vojvodina. Besides, it deals with the possibility of applying remediation treatments of contaminated sediment and with the efficiency of the different methods, that is the techniques, for immobilization of sediment heavy metals by applying S/S and thermal treatments. A dominant mechanism is proposed for the process of leaching ofthe metals from treated mixtures.Comparison of the results obtained by the different methods of sediment quality assessment showed that in some cases one approach to solving this problem is not  sufficient. Metal concentrations in particular sediment samples (the Begej, the DTD Canal, the Nadela, the Sava at Šabac) indicate the presence of contamination, the analyzed samples being of Class 4. According to the Dutch regulations, a sedimentof  Class 4 is of unacceptable quality and requires urgent intervention in the sense of sediment dredging, disposal into special depots, and, if possible, remediation. For some samples, despite a high pseudo-total concentration (Class 4), no potential toxicity was confirmed onthe basis of the ratioof the acidic volatile sulfide and simultaneously extracted metals. The results showed that, apart from chemical analyses, biological tests are also necessary, but also sequential extraction analysis, which can more clearly define the way of metal binding to the particular sediment fractions, to allow a more reliable prediction of metal mobility, potential toxicity and bioavailability. In the analysis of sediment quality it is also necessary toinclude the aspect of radioactivity, as it has been shown that the results of this analysis can, not only confirm some of the results of the other analyses, but also indicate the sediment age, origin of contamination and potential toxicity.The subsequent steps should be directed to the control and prevention of contamination, in order to ensure that the water course reviatalization has a lasting positive effect on the environment, an unimpared and safe navigation and application of remediation methods.In the sediment sample (Class 4) that was usedfor the examination of the efficiency of it appeared that zinc, nickel and lead exhibit a high risk, as the percentages of these metals in the exchangeable and carbonate phases were in the range from 40.1  to 45.2%. On the other hand, chromium and cadmium exhibited a moderaterisk, whereas copperin these fractions was present at the levels corresponding to a low risk (5.3%). This is alsoin agreement with the results of pore water analysis and simultaneously extracted metals and acid volatile sulphide examinations.The investigations presented in this work provided an answer to the question whetehr the remediation can successfully remove the contamination in the sense of the immobilization of metals in a state that will not be harmful tothe environment. All the treatments applied yielded a decrease of the percentage of cumulatively leached metals from the S/S mixtures, but none of the mixtures of treated sediments with the tested immobilization agents belongs to the group of inert materials if the cumulative leached concentrations are compared with the concntrations for the wastes given by the EU legislation (2003/33/EC). Ifthe goal is to obtain a non-hazardous material it is necessary to treat the contaminatedsediment with at least 30% of the immobilizing agent (cement or calcium oxide). Based on the diffusion coefficients and leachability index, the highest immobilization efficiency was achieved using a mixture of cement and calcium oxide (30% of cement and 10% of CaO) and by applying thermal treatment at a higher temperature (1100⁰C) with clay (20%). A dominant mechanism of leaching metals from these mixtures is diffusion.

Thesis (M.Sc.) -- University of Limpopo, 2005
Six aerobic bacterial strains [GM 10(1), GM 10 (2), GM 14, GM 15, GM 16 and GM 17] were isolated from an antimony mine in South Africa. Heavy-metal resistance and biosorptive capacities of the isolates were studied. Three of the isolates (GM 15, GM 16 and GM 17) showed different degrees of resistance to antimony and arsenic oxyanions in TYG media. The most resistant isolate GM 16 showed 90 % resistance, followed by GM 17 showing 60 % resistance and GM 15 was least resistant showing 58 % resistance to 80 mM arsenate (AsO4 3-). GM 15 also showed 90 % resistance whereas isolates GM 16 and GM 17 showed 80 % and 45 % resistance respectively to 20 mM antimonate (SbO4 3-). Arsenite (AsO2 -) was the most toxic oxyanion to all the isolates. Media composition influenced the degrees of resistance of the isolates to some divalent metal ions (Zn2+, Ni2+, Co2+, Cu2+ and Cd2+). Higher resistances were found in MH than in TYG media. All the isolates could tolerate up to 5 mM of the divalent metal ions in MH media, but in TYG media, they could only survive at concentrations below 1 mM. Also, from the toxicity studies, high MICs were observed in MH media than TRIS-buffered mineral salt media. Zn2+ was the most tolerated metal by all the isolates while Co2+ was toxic to the isolates. The biosorptive capacities of the isolates were studied in MH medium containing different concentrations of the metal ions, and the residual metal ions were determined using atomic absorption spectroscopy. GM 16 was effective in the removal of Cu2+ and Cd2+ from the contaminated medium. It was capable of removing 65 % of Cu2+ and 48 % of Cd2+ when the initial concentrations were 100 mg/l, whereas GM 15 was found to be effective in the biosorption of Ni2+ from the aqueous solutions. It was capable of removing 44 % of Ni2+ when the initial concentration was 50 mg/l. GM 17 could only remove 20 % of Cu2+ or Cd2+. These observations indicated that GM 16 could be used for bioremediation of xvi Cu2+ and Cd2+ ions from Cu2+ and Cd2+-contaminated aqueous environment, whereas GM 15 could be used for bioremediation of Ni2+.
National Research Foundation and the University of the North Research Unit

The research described in this doctoral thesis involves the experimental investigation of heteroepitaxial growth at quasicrystal surfaces. The aim is to further extend fundamental surface growth studies to such complex intermetallics and to form high quality, single-component quasicrystalline layers. The experiments included involve deposition of Cu, Bi, pentacene and carbon-60 on quasiperiodic surfaces. The formation and structure of these adsorbate layers on di�fferent quasicrystalline surfaces are analysed with surface science techniques. X-ray photoelectron spectroscopy measurements con�rmed complete �first layer followed by island growth mode of Bi on i-AlPdMn. Upon heating of the layer, stable monolayer and submonolayer coverages were observed supporting a strongly bound layer and the initial nucleation of stable, pentagonal clusters. Low energy electron di�raction patterns of the multilayer show that the {111}-rhombohedral islands are rotationally epitaxial with the substrate while the {012}-rhombohedral islands are not. The atomic structure and size of islands are measured with scanning tunnelling microscopy. A higher flux of Bi is found to inhibit the morphological transformation of the thin �film to {111}-rhombohedral islands. Scanning tunnelling microscopy of pentacene adsorption on i-AlPdMn found the molecules to be chemisorbed in a disordered, at layer at the surface. The same arrangement of molecules is observed for adsorption on a quasicrystalline Bi monolayer, while ordered rows of molecules are evidenced on the latter {012}- rhombohedral Bi islands. Pentacene formed incommensurate layers composed of dense, periodic rows, on the aperiodic vicinal Cu structure on i-AlPdMn. DFT calculations of naphthalene adsorption at the surface supported and detailed the adsorption sites of the acene along the rows. Cu exhibited 3-D cluster growth on i-AgInYb and on a pseudomorphic Bi layer at this surface. The Cu absorbs on the truncated, rhombic triacontrahedral clusters leading to some initial ordering. A pentacene monolayer on i-AgInYb successfully formed the �first epitaxial, quasiperiodic molecular overlayer to be observed experimentally. The layer is composed of many clusters with pentagonal symmetry and a large degree of orientational alignment along high symmetry directions of the substrate is observed. C60 grew in a disordered fashion on a Bi monolayer at i-AgInYb, although some local partial C60 clusters possessing 5- and 10-fold symmetry were observed at low submonolayer coverage.

In this thesis I present three papers on the Economics of the base metals industry. The thesis studies production, trading, and investment in the base metals industry, and thus explains some phenomena of the industry in an international context. Using the features of the base metals industry such as the practices in production and trading, physical properties, geology of the deposits and so on, we build theoretical models to simulate the behavior of the industry. In Chapter One, we study the determinants and the trend of base metals prices over time by an equilibrium model of supply and demand. Because the different types of natural resources exhibit different patterns of price changes in history, we particularly simulate the long run equilibrium to study the impacts of the determinants for base metals prices. The Cobb-Douglass production function on the supply side allows substitution among production factors. The demand function for base metals from the economy is also derived. In the long run, equilibrium of aggregate supply and demand determines the systematic price trend. We show how trends of base metals prices depend on technological progress, resource scarcity, natural resource tax, and the interest rate. Assuming constant returns to scale in base metals production, the price elasticity of the supply of base metals is relatively small. Interestingly, a high natural resource tax leads to a high price but low rate of price change over time. On the supply side, the decline of base metals relative prices can thus be explained by the inverse supply functions. On the demand side, the relative price is also declining over time as we see the implications of the inverse demand functions and our numerical illustrations. By solving the equilibrium condition, we show that the economic rent of base metals minerals in reserve may decline over time, or even not be valuable in future. The price elasticities of supply and demand are calculated and decomposed into specific effects. These are systematic components of base metal price changes in the world market. Chapter Two deals with the fluctuations in the prices of base metals. We consider the price in the short run as an equilibrium of trade. If the long run equilibrium regulates the prices and sets them in a stabilization, then the fluctuations in price are caused by the trade and speculative activities. By simulating speculative activities and optimizing the utility of agents in international exchanges, we show that the price fluctuations are the response to risk preferences of agents and the scale of international exchanges. We find out the critical point of production investment, which depends on the market demand, profitability of the metal industry, and the distribution of base metal minerals in nature. In the specific case of the industry versus the market condition when the uncertain production is above the critical point, the price of base metal fluctuates more or less according to the number of producer offers in base metal exchanges, the speculative activities, and risk preferences of agents. In contrast, if the investment level of the base metals industry in uncertain production is below the critical point, the effects of base metal exchanges scale to the price are in the reverse direction. The comparative statics inequalities are derived to clarify the responses of the price to the risk preferences of agents and scale of the international exchanges. Hence, the non-systematic changes of base metals prices in international exchanges are explained. Chapter Three studies the impact of the industrial and commercial processes on investment decisions in the base metals industry. The investment decisions of investors in the primary capital market and the stock price in the secondary capital market reflect properties of the base metals industry in capital markets. We present a model of investments, which is a two stage game that incorporates Hall-Jorgenson neoclassical investment analysis and properties of the base metals industry. The paper presents a set of explanatory parameters for the properties of base metal stocks and analyzes the investment decisions. We define the industry factor and explain the empirical observations on the beta coefficient of base metal stocks. The relationships between stock prices and base metals prices are clarified using the geology of base metals deposits. The results show that there is a strong impact of the industry factor on the volatility of base metal stock prices. Economies of scale in the mining industry lead to different effects of tax policy and output prices on investment decisions. We support conclusions of the model by evidence in the base metals industry. There are policy implications that are derived from the equations of the optimal investment. Key words : Base Metals, Price Fluctuations, Price Trends, Risk Aversion, Metals Industry, LME, International Exchange, Metal Stocks, Investment.

The electron density function of molecular systems supplies a package of information. Quantum mechanical methods of producing and analyzing this function have been significantly improved during the past few years. The advent of accurate pseudopotentials and corresponding basis sets for Kohn-Sham density functional and for post-Hartree-Fock electron-correlated approaches have enabled the inclusion of scalar relativistic and spin-orbit coupling effects as well as electron correlation effects into the electron density function. The unpacking of the information embedded in such a function via the quantum theory of atoms in molecules (QTAIM) became possible by utilizing the very new subshell fitting method of reconstructing the density distribution of core electrons that had been replaced by the pseudopotentials. These theoretical advances were applied in this thesis to characterize and explore the topological features of metal-metal bonding as one of the fundamental types of bonds formed between two elements. Group 11 and 12 transition metals which include gold and mercury as the most relativistic elements were the main focus of this work. Mono and poly-nuclear compounds (with up to 4 metal atoms) in both pure metal clusters and chloro-complexes were studied by ab initio MØller-Plesset perturbation calculations followed by QTAIM analysis on the relaxed density. Some of these chloro-complexes of copper, gold, zinc and cadmium metals were identified in the gas phase by mass spectrometric experiments. The general formulas of the set of molecules studied in group 11 were : M2, MCl, MCl+, MCl2, MCl2+, M2Cl+, M2Cl2^(s+), M2Cl3+, M3Cl2+, M3Cl3+, M3Cl5+, M4Cl5+ and M4Cl7+ and in group 12 were : M2, MCl, MCl+, MCl2, M2Cl3+, M3Cl5+, M4Cl7+ and M2^(s+). The topological features of metal-metal bonding were calculated along with atomic properties for each individual local minimum isomer found. The comparison of the metal-metal bonding within the complexes and with the dimers revealed new features of metal-metal bonding in 3d, 4d and 5d transition metal elements of groups 11 and 12. With the aid of strong correlation between bond dissociation energy and electron density at the location of the bond critical points found in the case of dimers, the strength of the metal-metal bonding in the complexes was estimated. The electron density’s basin properties calculated accurately for all the clusters and their isomers in this thesis provided more insight also into the nature of M-Cl bondings in the group 11 and 12 chloride clusters. Ultimately the bonding information was used to predict the viability of these clusters in the gas phase.
published_or_final_version
Chemistry
Doctoral
Doctor of Philosophy

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Atividades agropecuárias contribuem para a degradação das águas, alterando processos físico-químicos e biológicos, principalmente pela ocupação e uso do solo, por processos de lixiviação e/ou erosão. Os objetivos do presente trabalho foram: avaliar a influência do uso do solo na qualidade da água dos córregos Jaboticabal e Cerradinho e estudar o perfil metabólico da população microbiana da água. As coletas (C1 a C6) foram realizadas bimestralmente (Fev a Dez/2014) em oito pontos (P1 a P8), um deles situado na entrada do município de Jaboticabal, no córrego Cerradinho; outro, próximo à nascente do Córrego Jaboticabal; três pontos localizados em área urbana e os demais, em área rural. Foram determinadas variáveis físicas e químicas e a comparação metabólica da população microbiana das amostras de água foi realizada pela avaliação da capacidade de metabolização de diversas fontes de carbono pelo método EcoPlate (Biolog). Os resultados para oxigênio dissolvido, cloreto, nitrito, nitrato, sólidos totais dissolvidos e turbidez, estão de acordo com os valores estabelecidos na resolução 357/2005 do Conselho Nacional do Meio Ambiente (CONAMA), para corpos d´água classe 2. Em todos os pontos e coletas, o teor de fósforo total (Ptotal) excedeu o limite estabelecido pelo CONAMA. Em pontos próximos de atividades agrícolas ocorreram alterações nos valores de variáveis físicas e de variáveis químicas, observando-se resultados elevados para Ptotal e demanda química de oxigênio. A estatística multivariada auxiliou na interpretação dos resultados, mostrando que as atividades antropogênicas afetam a qualidade da água. O estudo de comparação das populações microbianas pela análise da capacidade de metabolização de diferentes fontes de carbono mostrou que a população microbiana da água parece não estar sendo alterada pelas atividades agrícolas. O perfil metabólico da população bacteriana das amostras não apresentou correlação com a presença das atividades agrícolas, os resultados mostram diferenças entre as coletas, mas não entre os pontos de amostragem. Atividades agropecuárias contribuem para a degradação das águas. Metais incorporados no solo, devido a diferentes manejos, podem ser transportados para as águas superficiais por processos de lixiviação e/ou erosão contaminando-as. Bactérias resistentes a metais podem ser utilizadas em processos de biorremediação. Objetivos: determinar as concentrações de metais traço em dois corpos d´água e no seu sedimento e isolar micro-organismos presentes na água para testes de resistência aos metais. As coletas de água (C1 a C6) foram realizadas bimestralmente (fevereiro a dezembro/2014) em oito pontos (P1 a P8). Um deles situado na entrada do município de Jaboticabal, no córrego Cerradinho; outro, próximo à nascente do Córrego Jaboticabal; três pontos localizados em área urbana e os demais, em área rural. O sedimento foi coletado na C6 nos pontos P3, P4, P6, P7 e P8. Nas amostras de água e sedimento foram determinadas as concentrações de cobre, cádmio, zinco, chumbo, níquel e cromo. Visando relacionar os teores de metais encontrados na água com os presentes no solo do entorno, foram coletadas (em fevereiro e agosto/2014), amostras de solo, em doze pontos (PS1 a PS12): PS1, PS2 e PS3, distantes do córrego Jaboticabal; PS4, PS5 e PS6 em área de plantação; PS7, PS8, PS9, PS10, PS11 e PS12, nas matas ciliares presentes nas imediações do córrego Jaboticabal. Foram isolados 182 micro-organismos das amostras de água e submetidos a testes de resistência aos metais estudados em meio de cultivo contendo diferentes concentrações (1, 2, 3, 4 e 5 mmol L-1) dos metais. Em pontos próximos ao córrego Jaboticabal foi possível observar maiores concentrações de metais no solo que, portanto, pode afetar a qualidade da água por meio de processos de erosão e/ou lixiviação, promovendo aumento da concentração de metais no corpo d’ água. Para a água observou-se reta de tendência com aumento nas concentrações de cádmio, cobre e cromo nos pontos da área agrícola (P6, P7 e P8). No sedimento, as maiores concentrações de metais foram encontradas em área agrícola evidenciando que o córrego está sendo impactado. Os micro-organismos isolados mostraram capacidade de se desenvolver mesmo na maior concentração estudada (5 mmol L-1) em proporções diferentes: para Zn (62,1%) e Pb (92,9%), Cd (32,4%) e Ni (29,7%), Cu (0,5%) e Cr (0%). Dos isolados resistentes 35 se desenvolveram em meio com quatro metais (Cd, Zn, Pb e Ni), mas apenas 1 isolado apresentou resistência aos cinco metais (Cu, Cd, Zn, Pb e Ni). Os microrganismos isolados precisam ser identificados e poderão ser utilizados em processos de biorremediação.
Farming activities contribute significantly to water degradation through alterations in physico-chemical and biological properties, which are mainly derived from land use and occupation as well as processes such as leaching and/ or erosion. This paper focused on assessing the influence of soil use on the water quality of surface waters of Jaboticabal and Cerradinho streams and study the metabolic profile of microbial communities found in this water body. Sampling dates (C1 to C6) were carried out bimonthly (from February to December of 2014) at eight different points (P1 to P8). One of these areas was set at the entrance of Jaboticabal city in Cerradinho stream. Another point lies near the source of the Jaboticabal stream. Three points were set within the urban area and the others within the rural area of Jaboticabal. Water physical and chemical variables were assessed. Moreover, we compared the ability of microorganisms to metabolize different sources of carbon using the Ecoplate method (Biolog). The results on dissolved oxygen, chloride, nitrite, nitrate, total dissolved solids and turbidity are in accordance with standards established by resolution number 357/ 2005 of the National Council on the Environment (CONAMA) for class 2 water bodies. The concentration of total phosphorus (TP) exceeded the limit value set by the CONAMA. We also noted significant changes on physical and chemical variables in areas near agricultural activities such as alterations of TP and chemical oxygen demand. Multivariate statistics assisted on data interpretation and showed the influence of human activities on water quality. Furthermore, the comparisons among microbial communities via study of metabolization of various carbon sources proved that farming activities have not affected the population structures. Therefore, the bacterial metabolic profile had no association with farming practices; however, the results showed differences among sampling dates, but not referring to the sampling points. Agricultural activities contribute to the degradation of the water bodies. Metals incorporated into the soil, due to different management, can be transported to the surface waters through the processes of lixiviation and / or erosion, contaminating them. Bacteria which are resistant to metals can be used in the bioremediation processes. Objectives: To determine the concentrations of trace metals in two a bodies of water and its sediment and isolate micro-organisms present in the water for testing their resistance to metals. The water sampling dates (C1 to C6) were carried out bimonthly (from february to december of 2014) at eight different points (P1 to P8). One of these areas was set at the entrance of Jaboticabal city in Cerradinho stream. Another point lies near the source of the Jaboticabal stream. Three points were set within the urban area and the others within the rural area of Jaboticabal. The sediment was sampling dates in C6 in the points P3, P4, P6, P7 and P8. For the water and sediment samples were determined the concentrations of copper, cadmium, zinc, lead, nickel and chromium. Aiming to relate the the levels of metals found in water with the ones present in the soil from the surroundings, were collected (in february and august / 2014), samples of the soil in twelve points (PS1 to PS12): PS1, PS2 and PS3, far from the stream Jaboticabal; PS4, PS5 and PS6 in plantation areas; PS7, PS8, PS9, PS10, PS11 and PS12,in riparian forests present in the stream nearby. 182 micro-organisms from the samples were isolated in the water samples and tested for resistance to the metals in culture media containing different concentrations(1, 2, 3, 4 and 5 mmol L-1) of metals. At points near the stream it was possible to observe higher metal concentrations in soil, therefore, may affect the quality of water through erosion and / or leaching, promoting increased concentration of metals in the body of water. For the water, the trend was observed with the increase in the concentrations of cadmium, copper and chromium in points of the agricultural area (P6, P7 and P8). In the sediment, the highest concentrations of metals were found in agricultural areas, showing that the stream is being impacted. The micro-organisms isolated showed the same ability to grow even in the highest concentration studied (5 mmol L-1) in different proportions: for Zn(62.1%) and Pb (92.9%), Cd (32.4%) and Ni (29.7%), Cu (0.5%) and Cr (0%). From the 35 isolated resistant organisms developed in medium with four metals (Cd, Zn,Pb and Ni), but only one isolate was resistant to the five metals (Cu,Cd, Zn, Pb and Ni). The microorganisms need to be identified and will be able to be used in bioremediation processes.

Thesis (m.s.)--University of Kentucky, 2004.
Title from document title page (viewed Jan. 5, 2005). Document formatted into pages; contains x, 112p. : ill. Includes abstract and vita. Includes bibliographical references.

"Semi-solid metal (SSM) processing has emerged as a preferred manufacturing method due to the superior quality associated with semi-solid castings. In recent years, the driving force to reduce process cost has led to the development of a few rheocasting (also termed slurry-on-demand) processes. These include UBE’s New Rheocasting (NRC) process [1], Idra Prince’s Semi-Solid Rheocasting (SSR) process [2], and THT’s Sub-Liquidus Casting (SLC®) process [3]. A novel slurry-making SSM process developed at ACRC/MPI, termed the “Continuous Rheoconversion Process” (CRP), is a passive liquid mixing technique in which the nucleation and growth of the primary phase are controlled using a specially designed “reactor”. The reactor provides heat extraction, copious nucleation and forced convection during the initial stage of solidification, leading to the formation of thixotropic structures. In these studies, the critical issues/challenges to optimize the CRP for industrial applications have been addressed through validation experiments and pre-industrial trials."

>Magister Scientiae - MSc
Transition metals are a group of metals which are light in weight and have high hydrogen solubility. Their interaction with hydrogen is exorthermic and this phenomenon makes them “ideal” candidates for various applications of hydrogen storage systems. This explains why the phenomenon of hydrogen storage in Pd is used as a model for hydrogen storage systems because of the nature of absorption associated with it (like a sponge even at low temperatures). The hydrogenation process can be conducted at either room or high temperatures in a furnace under low pressure-low hydrogen gas concentration-short hydrogenation time (LP-LC-ST) and in intelligent gravimetric analyser under high pressurehigh hydrogen gas concentration-long hydrogenation time conditions. Most of the research on hydrogen storage sytems is based on gravimetric analysis of absorbed and desorbed hydrogen concentration. In this work, a comparison study of the hydrogen content in pure Pd, Pd-Pt coated systems, Pd-Pt alloys, commercially pure Ti and Ti-6Al-4V alloy determined by gravimetric methods and elastic recoil detection analysis (which is based on the detection of recoiled hydrogen after interaction with He+ ions) technique was investigated. The changes in the structural properties and the hydrogen content of the materials when exposed to a hydrogen gas environment for different durations at various system temperatures and pressures will be reported. These changes have an effect on the microstructure of CP-Ti and Ti-6Al-4V alloy and structural properties of all the hydrogenated materials. The results obtained from optical microscopy, scanning electron microscopy, x-ray diffraction, intelligent gravimetric analyser, digital balance, elastic recoil detection analysis and Vickers hardness test, show the following: it is found that hydrogenation of Pd at elevated temperatures (550 ˚C and 650 ˚C) does not yield hydrides under LP-LC-ST conditions. However, at room temperature the absorption of hydrogen occurred faster at the beginning of the process. Furthermore, the absorption of hydrogen increased with pressure where optimum absorption (0.67 wt. % hydrogen concentration) occurred under a system pressure of 2000 mbar. After pressure release, the remaining hydrogen content in the Pd sample was 0.6 wt. %. The Pd-Pt coated system provide hydrogen mobility at 550 and 650 ˚C where hydrides were formed under LP-LC-ST conditions. In addition to the decrease of hydrogen solubility in Pd-Pt alloys with an increase in Pt content, the probability of the alloys to achieve full saturation also decreases with an increase in Pt content under HP-HC-LT conditions. CP-Ti and Ti-6Al-4V alloy absorb substantial amount of hydrogen in the first hour of room temperature hydrogenation under LP-LC-ST conditions but hydrides were not formed. Therefore, under LP-LC-ST conditions at room temperature, Pd is able to store hydrogen in the form of hydrides whereas Ti and Ti-6Al-4V alloy could not. The 550 ˚C is the optimum temperature for hydrogenation of CP-Ti under LP-LC-ST conditions. The Ti- 6Al-4V alloy absorb optimum hydrogen at 650 ˚C under LP-LC-ST conditions. Consequently, the change of microhardness of CP-Ti and Ti-6Al-4V alloy was found to depend on hydrogenation temperature.

The solid, liquid, and solidification properties of Pd, Ag pure metals and especially PdxAg1-x alloys are studied by using the molecular dynamics simulation. The effects of temperature and concentration on the physical properties of Pdx$Ag1-x are analyzed. Sutton-Chen (SC) and Quantum Sutton-Chen (Q-SC) many-body potentials are used as interatomic interactions which enable one to investigate the thermodynamic, static, and dynamical properties of transition metals. The simulation results such as cohesive energy, density, elastic constants, bulk modulus, pair distribution functions, melting points and phonon dispersion curves obtained for Pd, Ag and PdxAg1-x are in good agreement with the available experimental data at various temperatures. The predicted melting points of Pd, Ag and their binary alloys by using Q-SC potential parameters are closer to experimental values than the ones predicted from SC potential parameters. The liquid properties such as diffusion constants and viscosities computed from Q-SC potentials are also in good agreement with the available experimental data and theoretical calculations. Diffusion coefficients and viscosity results calculated from simulation obey the Arrhenius equation well. The coefficients of the Arrhenius equation are given in order to calculate the self-diffusion coefficient and shear viscosity of Pd-Ag alloys at the desired temperature and concentration. Using different cooling rates, we investigate glass formation tendency and crystallization of Pd-Ag metal alloys, by analyzing pair distribution function, enthalpy, volume, and diffusion coefficient. Pd-Ag alloys show the glass structure at fast cooling rates while it crystallizes at slow cooling rates. Glass and crystallization temperatures are also obtained from the Wendt-Abraham parameter. The split of the second peak in the pair distribution function is associated with the glass transition. Glass forming ability increases with increasing concentration of Ag in Pd-Ag alloys. Thermal and mechanical properties of Cu, Au metals and their ordered intermetallic alloys Cu3 Au(L12), CuAu(L10), and CuAu3(L12) are also studied to investigate the effects of temperature and concentration on the physical properties of Cu-Au alloys. The simulation results such as cohesive energy, lattice parameter, density, elastic constants, bulk modulus, heat capacity, thermal expansion, melting points, and phonon dispersion curves are in good agreement with the available experimental and theoretical data at various temperatures. The Q-SC potential parameters are more reliable in determining physical properties of metals and their random and ordered alloys studied in this work

Open pore metal foams with moderate porosity (0.6 – 0.7) may be of interest as regenerators due to their high volumetric heat capacity and large specific surface area. Replication process is a low cost and simple foam manufacturing method which provides moderate porosity metal foams. Due to its simplicity, it provides many opportunities to investigate the effect of porosity, pore size and shape or their combination. In this study, this process was used to manufacture metal foams. A method, called vacuum-gas, was the standard method for manufacturing metal foams in the University of Sheffield Material Science and Engineering department. This method was further investigated and two new methods, gas-only and mechanical infiltration, were introduced. Based on the foams produced by these methods, the gas-only method was adopted due to its repeatability and quality. The method was further investigated by manufacturing eight more samples (1.4-1.7 mm pore size) under various infiltration pressures and the optimum infiltration pressures were found for manufacturing foams with pore size of 1-1.1 mm, 1.4-1.7 mm and 2.0-2.36 mm. A total of nine aluminium metal foams were manufactured for thermal and pressure testing. The manufactured foams had three different pore sizes, 1-1.1 mm (called Small samples), 1.4-1.7 mm (called Mid samples) and 2-2.36 mm (called Large samples). On average foams had porosity in the range of 0.62 – 0.65. Since this type of metal foams never been tested as a regenerator, two extra samples (a packed bed of 10000 2mm ball bearing and a packed bed of 100 layers of wire mesh No. 200) were made to compare with the manufactured foams and the results from other researchers. A test rig was built to test the pressure drop under steady state flow condition from 1 to 6.5 m/s (permeability based Reynolds number from 20 to 175). The extended Darcy-Forchheimer equation and a cubic velocity of Darcy-Forchheimer were used to measure the permeability and form drag of the samples. The results showed that the cubic velocity equation had a better prediction of the permeability and form drag. The Small samples had the lowest permeability and highest form drag coefficient for metal foams. The wire mesh sample had the lowest permeability and lowest form drag among the tested samples. In addition to steady state flow, samples pressure drop was also measured under oscillatory flow. A test rig was built to measure pressure drop and air instant velocity under oscillatory flow (1 to 19 Hz). The results showed that the oscillatory pressure drop was higher than steady state flow except for the Small samples which had higher pressure drop at steady state flow. The pressure drop for the wire mesh sample was measured to compare with other researchers data and a good agreement was observed with some of the published data. Moreover, the instant air velocity was measured by a hot-wire anemometer inside the connecting tube between the sample holder and the compressor. The results showed that the air velocity behaved like a turbulent flow during the acceleration and deceleration period. A single-blow test rig was designed and manufactured to measure thermal performance of the samples. To estimate the average heat transfer coefficient of the samples, several types of the single-blow models were studied and the extended Schumann-Hausen model was implemented for predicting the samples’ outlet air temperature history. Two matching techniques, maximum gradient and direct curve matching were used to match the experimental and modelled outlet temperatures history to estimate samples’ NTU and average heat transfer coefficient. The results showed that NTU increased with decreasing of pore size. Based on mass flow rate Mid samples had the highest h, however the difference between the metal foam samples were insignificant. The foam samples had higher heat transfer coefficient than the ball bearing sample but the wire mesh sample had the highest heat transfer coefficient. The heat transfer results for the wire mesh and ball bearing samples were compared with published data and good agreements were observed.

Thesis (M.S.)--West Virginia University, 2004.
Title from document title page. Document formatted into pages; contains ix, 87 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 66-68).

Thesis (MTech (Environmental Health))--Cape Peninsula University of Technology, 2017.
Surface water is used as a source of water supply in many countries, including South Africa. One of the sources of surface water pollution is leachate and surface runoff from landfills. In agricultural soils, the landfill runoff and leachate deteriorate the quality and affect the fertility of soil. The entry of metals and microorganisms from landfill leachate to adjacent environments is through surface runoff due to rainfall. Adverse effects on human- and environmental health triggers a need to monitor and control contaminants in the environment. The aims of the study are to determine the effect of landfill runoff and leachate on agricultural soil and river water (Veldwachters River) running adjacent to the Devon Valley landfill site and to identify potential metal-tolerant organisms in environmental samples collected in Stellenbosch, Western Cape, South Africa. Samples (agricultural soil, river water and sediments) were collected once a month for a period of six months from the study area for analysis. Physicochemical parameters that are known to have major effects on environmental samples were assessed and the concentrations of various metals (Al, Pb, Cr, Mn, Mo, Co, Ni, Cu, Zn, Fe, Cd and V) were also determined by means of inductively coupled plasma mass spectrometry (ICP-MS). Soil texture analysis was tested in order to monitor the metal distribution in soils under the influence of environmental factors.

Os objetivos deste estudo foram avaliar a concentração de Cd, Pb, Cr e Ni nos tecidos da cana-de-açúcar, constatar a presença de bactérias fixadoras de nitrogênio (BFN) na variedade IAC87-3396 cultivada em ambiente com altas concentrações de metais e avaliar a tolerância das bactérias metais pesados \"in situ\" e \"in vitro\". A cana-de-açúcar IAC87-3396 foi cultivada em área com altos teores de metais. Antes do plantio foram aplicados 5 mitigadores de metais pesados. Para detecção e quantificação de níquel, chumbo, cromo e cádmio foram realizadas análises em ICP-MS em amostras de tecidos da cana-de-açúcar (folha +1, raízes e tolete pré-germinado) obtidos na colheita da cana-planta e cana-soca. A quantificação das bactérias foram realizadas em amostras da parte aérea e das raízes, da cana-planta (colheita) e da cana-soca (6 meses e colheita), utilizando a metodologia do tolete pré-germinado. O ensaio \"in vitro\" consistiu em acrescentar ao meio de cultura 4 concentrações de Pb, Cd, Ni e Cr inseridos isoladamente e em combinações e proceder a inoculação em placa de petri de 4 bactérias (Herbaspirillum seropedicae, Gluconacetobacter diazotrophicus, Azospirillum amazonense e Burkholderia tropica). O comportamento nas diferentes concentrações foi avaliado atribuindo-se valores aos diferentes padrões de crescimento. Para os metais, a maior concentração foi encontrada nas raízes e a menor foi encontrado na folha +1. No campo os valores da folha +1 aumentaram da cana planta para a cana soca e os valores das raízes diminuíram. Comparando campo e tolete pré-germinado, na cana planta a concentração nas raízes foi menor do que o encontrado no campo e na parte aérea o tolete teve uma concentração maior para o Ni e Cd. Na cana soca o campo possui as maiores concentrações tanto para parte aérea como para raízes. Na quantificação das bactérias, a comparação entre os períodos mostrou que a quantificação no geral é maior na cana planta. Na cana planta a quantificação foi maior na parte aérea, no 6 meses da cana soca o predomínio é na raiz e na colheita da cana soca existe uma distribuição mais uniforme das bactérias no interior da planta. No ensaio \"in vitro\" a concentração máxima de metais tolerada foi a máxima estudada para Pb (248 mg L-1), Cd (8 mg L-1) e Ni (40 mg L-1). O Cr e a associação entre 2, 3 e 4 metais proporcionaram o não crescimento das bactérias. Para a maior parte das bactérias houve associação significativa entre os padrões de crescimento e as concentrações de metais no meio de cultura. Na variedade IAC87-3396 foram encontrados os 4 gêneros de BFN, mesmo nas raízes onde os teores de Pb, Ni, Cr e Cd foram maiores. A tolerância das BFN aos metais \"in situ\" diferiu da \"in vitro\". O cromo e a associação entre os metais limitaram o crescimento \"in vitro\" de todas as bactérias. A metodologia do tolete pré-germinado não refletiu as condições de concentração de metais em materiais coletados no campo. A cana-deaçúcar tem potencial para ser uma cultura fitoextratora e acumuladora de Pb, Ni, Cr e Cd
The objectives of this study were to evaluate the concentration of Cd, Pb, Cr and Ni in the tissues of sugarcane, noting the presence of the BFN in IAC87-3396 variety grown in contaminated environment and evaluate the BFN tolerance to heavy metals \"in situ\" and \"in vitro\". Sugarcane variety IAC87-3396 was grown in an soil contaminated by metals. Before planting, five mitigators of heavy metals were applied. Analysis were performed to detect nickel, lead, chromium and cadmium in tissues of sugarcane, including leaf +1, roots and pregerminated sett (shoot and root) at harvest of the plant cane and ratoon cane. To quantify the nitrogen-fixing bacteria, three tests were performed comprising the shoots and roots, one in the plant cane (at harvest) and two in ratoon cane (6 months and harvesting) using the methodology of pre-germinated sett. The test \"in vitro\" consisted of adding to the culture medium Pb, Cd, Ni, Cr, mixed metals and inoculated in a petri dish of 4 bacteria (Herbaspirillum seropedicae, Gluconacetobacter diazotrophicus, Azospirillum amazonense and Burkholderia tropica). The behavior in different concentrations was evaluated by assigning values to different growth patterns. For all metals, the highest concentration was found in the roots and the lowest values were found in leaf +1. This values in leaf +1 increased from plant cane to ratoon cane while in root it decreased. In relation to the pregerminated sett, metal concentration in root of plant cane was lower than that found in the field while the leaf had a higher concentration only for Ni and Cd. The field ratoon cane has the highest concentrations for both the aerial and root part. For the quantification of bacteria, the comparison between the measurement periods showed that in general it is greater in the plant cane. The location of bacteria inside the plant revealed that, in the plant cane, it was higher in the shoot. However, for the first six months of ratoon cane the predominance of bacterias was in the root. At harvest of the ratoon crop a more uniform distribution of bacteria was found inside the plant. In the \"in vitro\" essay the maximum concentration studied was the maximum tolerated for Pb (248 mg L-1), Cd (8 mg L-1) and Ni (40 mg L-1). The association between Cr and 2, 3 and 4 metals provided no growth of bacteria. For most of the bacteria a significant association was found between growth patterns and concentrations of metals in the culture medium. All the four kinds of NFB were found in IAC87-3396 even in roots where the levels of Pb, Ni, Cr and Cd were high. The tolerance of the NFB to these metals \"in situ\" is different from that \"in vitro\". The chromium and its association with other metals have limited growth \"in vitro\" of all bacteria. The methodology of pre-germinated sett did not reflect the conditions of metal concentration in material collected in the field. Sugarcane plant has the potential to be a culture of phytoextraction and accumulation of Pb, Ni, Cr and Cd

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Os metais terras-raras (TRs) apresentam um alto valor agregado, o qual não provém de sua baixa ocorrência mineral, mas sim da dificuldade na separação destes pelos métodos clássicos, uma vez que os elementos desta série apresentam semelhantes comportamentos físico-químicos. Desta maneira, altos custos são despendidos anualmente para a obtenção das TRs na forma pura, sendo esta necessária para as suas aplicações tecnológicas. Uma alternativa a esta problemática é o emprego da biossorção, a qual apresenta potencial aplicação para a extração e separação de metais valiosos, por ter como vantagem uma alta eficiência agregada a um baixo custo. Alguns requisitos são necessários para que o processo de biossorção possa ter competitividade técnica e econômica, tais como, o material biológico empregado deve apresentar um baixo custo, sendo assim necessário estabelecer as condições ótimas de cultivo do micro-organismo para sua produção em larga escala, e também a utilização do biossorvente na forma imobilizada possibilita seu uso como um adsorvente convencional, o qual apresenta tamanho desejado, alta porosidade e um bom desempenho físicoquímico. Por esta razão, o presente trabalho teve como principal objetivo avaliar a potencialidade de utilização da biomassa melanizada (inativa) obtida da linhagem mutante MEL 1 do fungo Aspergillus nidulans, na sua forma livre e imobilizada, no processo de biossorção dos metais terras-raras neodímio, lantânio e cério em soluções monometálicas. Com os resultados obtidos foi possível estabelecer a condição ótima de cultivo da linhagem MEL 1 do A. nidulans que proporcionou uma biomassa mais melanizada, a qual apresentou uma maior capacidade biossortiva. Para tal condição, a massa micelial obtida após o crescimento do fungo por três dias, sob agitação à...
The rare-earth metals (TRs) have a high added value, which does not come from its low mineral occurrence, but the difficulty in separating these by classical methods, since the elements of this series show similar physical and chemical behavior. Thus, high costs are spent annually to obtain the TRs in pure form, which is necessary for their technological applications. An alternative to this problem is the use of biosorption, which has potential application for extraction and separation of valuable metals, having the advantage of a high aggregate efficiency at a low cost of production. Some requirements are necessary for the biosorption process may have technical and economic competitiveness, such as the biological material used must be low cost and it is necessary to establish the optimum conditions for cultivation of the microorganism to its large scale production, and also the use of biosorbent immobilized in the form enables its use as a conventional adsorbent, which has the desired size, high porosity and good physical and chemical performance. For this reason, this study aimed to evaluate the potential use of biomass melanized inactive mutant of the fungus Aspergillus nidulans MEL1 in its free form and immobilized in calcium alginate, in the process of biosorption of neodymium rare-earth metals, lanthanum and cerium. The results concerning the kinetics of biosorption showed that the ability of TRs biosorptive varied between different forms of biomass, and this capacity was higher compared to free biomass immobilized. Regarding the maximum biosorption capacity (Qmax), we observed that the immobilized biomass caused a reduction in Qmax of lanthanum and neodymium in approximately 60 and 33% respectively, have kept their Ce Qmax for both types of biomass (open and immobilized). The affinity of biomass... (Complete abstract click electronic access below)

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Este trabalho descreve as sínteses e caracterizações de silsesquioxanos organofuncionalizados com tiouréia (T8-Pr-TU), 2,2’-dipiridilamina (T8-Pr-DPA) e 2-Amino-1,3,4-Tiadiazol (T8-Pr-ATD). Os materiais foram caracterizados por: espectroscopia na região do infravermelho (FTIR), ressonância magnética nuclear 29Si e 13C no estado sólido (RMN) e análise elementar. Nos estudos de batelada para os materiais, foram utilizados os íons metálicos de Cd (II), Cu (II), Ni (II) e Co (II) e os solventes foram água e etanol. Determinou-se a dose de adsorvente na solução e o tempo de equilíbrio, na qual, para o material T8-Pr-TU em todos os meios e metais, a capacidade máxima de adsorção ocorreu em 50 mg de adsorvente, e o equilíbrio de adsorção foi de aproximadamente 9 minutos para todos os solventes e íons metálicos, enquanto que, para o T8-Pr-DPA em todos os meios e metais, a capacidade máxima de adsorção ocorreu com 10 mg de adsorvente e tempo de equilíbrio de 10 minutos; já para o T8-Pr-ATD, independentemente do solvente e dos metais, a capacidade máxima de adsorção foi em 50 mg de adsorvente e tempo de equilíbrio de 10 minutos. Estudou-se ainda a capacidade máxima de adsorção (Nf) para os solventes, na qual a capacidade máxima se deu em meio etanólico > aquoso. O efeito dos contra-íons Cl-, Br- e ClO4- foi estudado para todos os materiais, na qual observou-se que para os três adsorventes a capacidade de adsorção seguiu a seguinte ordem: Cl- > Br- > ClO4-. Em seguida, as isotermas de adsorção foram ajustadas pelos modelos Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Para cinética de adsorção dos metais, foram usados três modelos cinéticos como pseudo-primeira-ordem, pseudo-segunda-ordem e Elovich. Os modelos de Langmuir e Elovich foram os mais apropriados para descrever os dados...
This work describes the synthesis and characterization of silsesquioxanes organofuncionalizados with thiourea (T8-Pr-TU), 2,2 '-dipyridylamine (T8-Pr-DPA) and 2-Amino-1,3,4-thiadiazole (T8-Pr-ATD). The materials were characterized by infrared spectroscopy (FTIR), nuclear magnetic resonance 29Si and 13C solid state (NMR) and elemental analysis. In studies to batch materials were used for metal ions of Cd (II), Cu (II), Ni (II) and Co (II) and the solvents were water and ethanol. It was determined the dose of adsorbent in the solution and equilibrium time in which, for the material T8-Pr-TU in all ways and metals, the maximum adsorption capacity observed in 50 mg of adsorbent, and adsorption equilibrium was about 9 minutes for all metal ions and solvents, whereas for T8-Pr-DPA in all ways and metals, the maximum adsorption capacity was 10 mg of adsorbent and equilibration time of 10 minutes, whereas for T8-Pr-DPA, regardless of solvent and metals, the maximum adsorption capacity was 50 mg of adsorbent and equilibration time of 10 minutes. It was also studied the maximum adsorption capacity (Nf) for solvents, in which the maximum capacity was in ethanolic > aqueous. The effect of the counter ions Cl-, Br-and ClO4- was studied for all materials in which it was observed that the three adsorbents for the adsorption capacity followed the order: Cl-> Br-> ClO4-. Then the adsorption isotherm models were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (DR). For adsorption kinetics of metals, three kinetic models were used as pseudo-first-order, pseudo-second-order and Elovich. The Langmuir model and Elovich were most suitable to describe the data and kinetics of adsorption, respectively, of all materials. From the model isotherm DR, one can calculate the free energy (E)... (Complete abstract click electronic access below)

Orientador: Marcelo Ferraz Mesquita
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba
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Resumo: Este trabalho avaliou a resistência à tração e alongamento de amostras de diferentes diâmetros (1,5, 2,0 e 5,0 mm) fundidas em titânio comercialmente puro (Tritan - Dentaurum), submetidas a soldagem a laser em diferentes distâncias de soldagem (0,0 mm e 0,6 mm). Foram confeccionadas 45 amostras, separadas em 9 grupos (n= 5): G1) diâmetro 1,5 mm controle (não submetidas à soldagem); G2) diâmetro 1,5 mm e distância zero; G3) diâmetro 1,5 mm e distância 0,6 mm; G4) diâmetro 2,0 mm (controle); G5) diâmetro 2,0 mm e distância zero; G6) diâmetro 2,0 mm e distância 0,6 mm; G7) diâmetro 5,0 mm (controle); G8) diâmetro 5,0 mm e distância zero; e G9) diâmetro 5,0 mm e distância 0,6 mm. Após a fundição, todas as amostras, exceto as dos grupos controle, foram seccionadas e unidas, utilizando-se resina acrílica autopolimerizável, para a soldagem com as seguintes especificações: 320V / 9 milisegundos (ms) (amostra de 1,5mm), 330V / 9 ms (amostra de 2,0mm) e 350V / 9 ms (amostra de 5,0mm) em um aparelho de soldagem a laser Desktop-F (Dentaurum KG). Após a soldagem, foram submetidas ao ensaio de resistência à tração até a ruptura em máquina servohidráulica (MTS 810) com velocidade de 1mm/min. As superfícies de fratura foram analisadas em microscópio eletrônico de varredura (M.E.V. ¿ JEOL). Os resultados foram submetidos à Análise de Variância e teste de Tukey (p<0,05). Os valores médios de resistência máxima à tração (MPa) revelaram que o grupo controle apresentou valores, para todos os diâmetros, estatisticamente superiores aos grupos experimentais, que não diferiram entre si, exceto para 5,0 mm de diâmetro, onde a distância de 0,6 mm apresentou maiores valores (G1- 595,64; G2- 496,46; G3- 441,04; G4- 516,54; G5- 397,85; G6- 442,15; G7- 560,19; G8- 200,88; e G9- 316,04). Os valores médios de alongamento (mm) para o grupo controle foram estatisticamente superiores aos experimentais nos diâmetros 2,0 e 5,0 mm, não havendo diferença entre os grupos no diâmetro 1,5 mm. Não houve diferença estatística entre os grupos experimentais (G1- 1,68; G2- 1,47; G3- 1,20; G4- 2,61; G5- 1,34; G6- 1,05; G7- 2,51; G8- 0,92; e G9- 1,32). As imagens revelaram eficiente penetração do laser nas amostras de 1,5 e 2,0 mm de diâmetro, e insuficiente nas de 5,0 mm de diâmetro. A resistência à tração para todos os diâmetros e o alongamento para os diâmetros 2,0 e 5,0 mm foram influenciados pela técnica de soldagem a laser de forma significativa. Dentre as amostras de 5,0 mm de diâmetro submetidas à soldagem a laser, aquelas com distância de 0,6 mm entre as partes apresentaram maior alcance do feixe de laser
Abstract: The aim of this study was to evaluate the tensile strength and elongation of commercially pure titanium samples (Tritan - Dentaurum), with 3 diameters (1.5, 2.0 and 5.0 mm of diameter x 42 mm length), submitted to laser welding in 2 distances of soldering (0.0 mm and 0.6 mm). 45 samples were made (dumbbell), divided in 9 groups (5 each): G1) 1.5 mm control (without welding procedures); G2) 1.5 mm and no distance; G3) 1.5 mm and 0.6 mm of distance; G4) 2.0 mm (control); G5) 2.0 mm and no distance; G6) 2.0 mm and 0.6 mm; G7) 5.0 mm (control); G8) 5.0 mm and no distance; G9) 5.0 mm and 0.6 mm of distance. After casting, all the samples, except control groups, were sectioned and joined with self curing acrylic resin for the welding procedures, as follows: 320V/9 miliseconds (ms) (samples of 1.5mm), 330V/9ms (samples of 2.0 mm) and 350V/9ms (samples of 5.0 mm) using a laser welding machine Desktop-F (Dentaurum KG). After soldering, the samples were submitted to tensile test using a servohidraulic machine MTS-810 with speed of 1mm/min. The fractured surfaces were microscopically analyzed (M.E.V. ¿ JEOL). Data were submitted to ANOVA and Tukey¿s test (p<0.05). The tensile strength mean values (MPa) for control group were statistically higher than the experimental groups, which did not differ from each other, except for 5.0 mm group, in which the samples with 0.6 mm of distance had the highest values (G1- 595.64; G2- 496.46; G3- 441.04; G4- 516.54; G5- 397.85; G6- 442.15; G7- 560.19; G8- 200.88 and G9- 316.04). The mean values of elongation (mm) for the control group were statistically higher than experimental groups in the 2.0 and 5.0 mm, having no difference for the groups with 1.5 mm. There was no difference between the experimental groups (G1- 1.68; G2- 1.47; G3- 1.20; G4- 2.61; G5- 1.34; G6- 1.05; G7- 2.51; G8- 0.92; and G9- 1.32). The SEM images showed a good penetration of laser in the samples of 1.5 and 2.0 mm of diameter, and insufficient penetration of laser in the samples of 5.0 mm. Ductile fractures were predominant in all groups with the presence of dimples. Laser welding procedure is an effective method of joining titanium, however, caused a decrease in the values of tensile strength for all diameters and elongation for 2.0 and 5.0 mm. Among the 5.0 mm samples submitted to laser welding procedures, the laser welding was more effective for the samples with distance of 0.6 mm between the parts
Doutorado
Protese Dental
Doutor em Clínica Odontológica

Orientadores: Meuris Gurgel Carlos da Silva, Sirlei Jaiana Kleinübing
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Pesquisas no campo da tecnologia têm buscado avaliar técnicas e/ou processos econômicos e eficientes para o tratamento de efluentes que contenham metal pesado. Atualmente a bioadsorção vem se apresentando como uma boa alternativa às tecnologias existentes. Este trabalho teve como objetivo a investigação da macrófita Azolla pinnata como bioadsorvente de cinco íons metálicos: Cd2+, Cu2+, Ni2+, Pb2+ e Zn2+ em soluções sintéticas. A caracterização do biomaterial foi realizada utilizando-se técnicas como Microscopia Eletrônica de Varredura (MEV) para análise da superfície do material; análise de Espectroscopia de Energia Dispersiva de Raios-X (EDX), que mostrou que qualitativamente a diminuição de íons de competição (Ca, Na e K) após o processo de adsorção, evidenciando que a troca iônica pode ser um dos mecanismos do processo; e análise de Infravermelho por Transformada de Fourier (FTIR), em que se pôde constatar que alguns grupos funcionais como carboxilas e grupos sulfonados são fundamentais no processo. A cinética de adsorção foi ajustada pelos modelos de pseudoprimeira e pseudossegunda ordem, sendo que o melhor ajuste variou de acordo com o íon estudado. O modelo de difusão intrapartícula mostrou que muitos mecanismos podem ser limitantes na taxa com a qual ocorre o processo. Os dados de equilíbrio foi ajustado pelos modelos de isoterma de Langmuir e de Freundlich em duas temperaturas, 25 e 45 ºC. O processo foi favorecido pelo acréscimo de temperatura para todos os íons. O modelo de Langmuir se ajustou melhor aos dados experimentais de todos os íons e o valor de capacidade máxima de adsorção (qmax) a 25 ºC foi de 0,359; 0,448; 0,254; 0,472 e 0,357 mmol/g para Cd2+, Cu2+, Ni2+, Pb2+ e Zn2+, respectivamente. Os eluentes HCl, EDTA e CaCl2 foram testados no processo de dessorção em batelada e o cloreto de cálcio se mostrou eficiente além de não causar danos ao material nem diminuir a capacidade de adsorção da macrófita. Ensaios dinâmicos em coluna de leito fixo foram realiados para os íons Cu2+ e Pb2+ com soluções mono e bicomponentes. Nos ensaios em sistema binários, pode-se constatar uma grande preferência pela adsorção de íons chumbo e, portanto, uma grande queda na adsorção de cobre. Foram testados ciclos de adsorção/dessorção em coluna utilizando o CaCl2 como eluente e, em três ciclos, a macrófita manteve suas propriedades adsortivas. Com estes resultados, pode-se constatar que a realização deste trabalho contribuiu para a avaliação deste material como bioadsorvente alternativo e que, especificamente, macrófita A. pinnata mostrou-se atrativa para utilização nos processos de tratamento e/ou estabilização de metais pesados presentes em baixas concentrações em efluentes industriais
Resumo: No processo Kraft para produção de papel e celulose, os cavacos de madeira são cozidos em um digestor com uma solução aquosa denominada licor branco, constituída de hidróxido de sódio (NaOH) e sulfeto de sódio (Na2S). Durante o cozimento uma pasta fibrosa é produzida. Esta pasta é filtrada e segue para o branqueamento. O produto filtrado chama-se licor negro, devido à mudança da sua cor nesta etapa. O licor negro possui aproximadamente 15 % de sólidos em massa. Ele é bombeado para a unidade de recuperação, na qual ele será concentrado em evaporadores de múltiplosefeitos até 75 % de sólidos em massa. Em seguida, ele é bombeado para uma caldeira onde é queimado, para recuperar os sais inorgânicos e, principalmente, fornecer calor para geração de calor. Durante a evaporação do licor negro, quando a porcentagem em sólidos ultrapassa 50 %, ocorre a precipitação de sais inorgânicos. Estes sais se depositam nas superfícies de troca térmica dos evaporadores diminuindo sua eficiência e causando prejuízos à indústria. Os principais sais que causam este problema são o carbonato de sódio (Na2CO3) e o sulfato de sódio (Na2SO4). O objetivo do presente trabalho foi testar e validar um método experimental para a determinação da quantidade de Na2CO3 presente em amostras industriais de licor negro. Além disso, também foram analisadas algumas propriedades físico-químicas do licor negro, como massa específica, teor de sólidos e viscosidade. Com os resultados obtidos, tentou-se obter uma correlação entre o teor de carbonato de sódio e as demais propriedades do licor que foram determinadas. Os resultados das análises das características físico-químicas demonstraram coerência e boa reprodutibilidade, porém, os resultados das análises de teor de carbonato de sódio não foram satisfatórios e mostraram que a técnica deve ser aperfeiçoada
Abstract: Research in the technology field has been looking for evaluating efficient and economic techniques and/or process for effluents that contains heavy metal. The biodsorption process has been seemed as a good alternative to the existing technology. This work had the aim to investigate the use of Azolla pinnata macrophyte as biosorbent of five metallic ions: Cd2+, Cu2+, Ni2+, Pb2+ and Zn2+ in synthetic solutions. The biomaterial characterization was carried out by techniques as scanning electron microscopy (SEM) for the analyze of material superficies; the energy dispersive X-ray spectroscopy (EDX), which showed, qualitatively, a decreasing in the competitions ions (Ca, Na e K) after the sorption process, indicating that the ion exchange can be one o the process mechanism; and Fourier Transform Infrared Spectroscopy (FTIR), in which it was possible implied functional groups as carboxyl and sulfonate play a important role in the adsorption. The kinetics was adjusted by primer and second order models and the model which fit better depends on each ion. The intra-particle diffusion model showed that several mechanisms may be limiting to the process rate. The equilibrium data were adjusted by Langmuir and Freundlich models in two temperatures: 25 and 45 ºC. The process was favored by the increasing in the temperature for all five ions. The Langmuir model fit better the experimental data and the maximum adsorption capacity (qmax) were 0,359; 0,448; 0,254; 0,472 and 0,357 mmol/g for Cd2+, Cu2+, Ni2+, Pb2+ and Zn2+, respectively. The HCl, EDTA and CaCl2 eluents were tested in the desorption process and the calcium chloride was efficient and did not cause any damage in the biomaterial or decreasing the biosorption capacity. Dynamics runs were carried out in fixed-bed in mono and bi-components solutions. In the binary were found a great preference for lead instead of copper and as a result, a significant decrease in the removal of copper. Adsorption/desorption cycles were tested in fixed-bed system using CaCl2 as eluent. After three cycles no damage, weight lost or significant decrease in the biosorption capacity was noticed. These results indicating that the A.pinnata macrophyte is an attractive potential new biosorbent to be used in heavy metal removal especially in low concentrations effluents
Abstract: In the Kraft process for pulp and paper production, wood chips are cooked in a digester with an aqueous solution named white liquor, consisted by sodium hydroxide (NaOH) and sodium sulfide (Na2S). During this cooking process, wood chips are transformed generating a fibrous paste and a liquid solution. This paste is filtered and separated from the liquid solution, named black liquor due to its color. The paste goes to the bleaching stage to produce cellulose. Black liquor contains inorganic and organic (mainly lignin) compounds from wood. Initially this black liquor contains approximately 15 mass/% of solids and is sent to the recovery unit to have this concentration raised to approximately 75 mass/% to be burned in a recovery boiler in order to generate power and recover inorganic reactants, recycling them to the process. The concentration process of black liquor occurs in a multiple effect evaporators unit. During this process, when the concentration of solids exceeds 50%, the precipitation of inorganic salts (mainly Na2CO3 and Na2SO4) begins. These salts are deposited in the heat transfer surfaces of the evaporator tubes, reducing their efficiency, leading to a reduction in the production capacity. The scope of this work was testing and validate an experimental method to estimate the content of Na2CO3 present in industrial black liquor samples. Moreover, some black liquor's physical-chemical properties as density, solids content and viscosity were also analyzed. An attempt to develop a predictive model to evaluate sodium carbonate content from the other properties was made. The results obtained for physical-chemical properties have shown a good consistency. However, the results of sodium carbonate analyses were not satisfactory, showing that the technique must be improved
Mestrado
Engenharia de Processos
Mestra em Engenharia Química

Os fertilizantes fosfatados produzidos no Brasil são obtidos principalmente pelo processamento por via úmida da rocha fosfática ígnea com ácido sulfúrico concentrado, gerando como produto final o ácido fosfórico e como subproduto o sulfato de cálcio di-hidratado (fosfogesso ou gesso agrícola). Parte do fosfogesso gerado é estocada em pilhas a céu aberto e parte vem sendo utilizada na agricultura como condicionador de solos. Para garantir utilização segura do fosfogesso na agricultura é importante a determinação dos teores de impurezas, em particular os metais, presentes no mesmo. Neste trabalho foram determinadas as concentrações dos metais (As, Ba, Cd, Cr, Co, Cu, Hg, Ni, Pb, Se, Zn e elementos terras raras - ETR) presentes no fosfogesso (FG) e nos fertilizantes superfosfato simples (SSP), superfosfato triplo (TSP), fosfato monoamônio (MAP) e o di-amôniofosfato (DAP) produzidos no Brasil. Os metais Cd, Cu, Ni, Pb e Zn foram determinados de acordo com a metodologia EPA 3052. Os mesmos metais, As e Se também foram determinados de acordo a metodologia EPA 3050B, recomendada pelo Ministério da Agricultura, Pecuária e Abastecimento (MAPA). Todos estes metais possuem limites máximos de concentração estabelecidos pelo órgão de meio ambiente estadual, Companhia Ambiental do Estado de São Paulo (CETESB), e/ou pelo MAPA. As duas metodologias apresentaram valores de concentração diferentes para os metais analisados. Ba, Co, Cr e ETR foram determinados pela técnica de análise por ativação neutrônica instrumental (INAA). Avaliou-se também a disponibilidade dos metais As, Cd, Cr, Co, Cu, Ni, Pb, Se e Zn para o meio ambiente determinando-se a concentração destes por meio de metodologia estabelecida pela Comunidade Européia. Todos os resultados obtidos para as amostras de fosfogesso estão abaixo dos limites estabelecidos pelo MAPA e pela CETESB. As concentrações dos metais presentes no fosfogesso são menores do que os valores encontrados nos fertilizantes fosfatados estudados. Esta última metodologia mostrou que os metais presentes nas amostras estão muito pouco disponíveis para o meio ambiente. Os resultados atestam a aplicação segura deste subproduto nos solos agrícolas quanto ao quesito de contaminação por metais.
The Brazilian phosphate fertilizer is obtained by wet reaction of the igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid, and dehydrated calcium sulphate (phosphogypsum) as by-product. Part of this phosphogypsum is stored in stacks at open air and part has been used in agriculture, as soil amendment. To assure a safe utilization of phosphogypsum it is important to determine the levels of impurities, particularly of metals, present in phosphogypsum. In this paper, the concentration of metals (As, Ba, Cd, Cr, Co, Cu, Hg, Ni, Pb, Se, Zn and rare earth elements) present in Brazilian phosphogypsum and also in single super phosphate (SSP), triple super phosphate (TSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP) were determined. The metals Cd, Cu, Ni, Pb and Zn were determined following the procedure EPA 3052. The same elements, As and Se were also determined following the procedure EPA 3050B, recommended by Ministério da Agricultura, Pecuária e Abastecimento (MAPA). All these metals are controlled by environmental and agriculture regulation institutes in Brazil. The concentrations obtained for the metals analyzed by using the two procedures were different. Ba, Co, Cr and rare earth elements were determined by neutron activation analysis. In order to evaluate the availability of these metals As, Cd, Cr, Co, Cu, Ni, Pb, Se and Zn to the environment, the content of the same elements were determined following a procedure established by the EC (European Community), which includes an initial attack of the samples with EDTA-NH4 0.05M, at pH 7.0. In all these cases, phosphogypsum presented metals concentration lower than the phosphate fertilizers, and the results are below the limits adopted by MAPA and Companhia Ambiental do Estado de São Paulo (CETESB). The results obtained using the methodology with mild attack show that the metals are not available to the environment, giving evidence that the application of phosphogypsum in agriculture is safe as far as contamination by metals.

Orientador: Newton Luiz Dias Filho
Banca: Fauze Ahmad Aouada
Banca: Douglas Cardoso Dragunski
Resumo: Este trabalho descreve as sínteses e caracterizações de silsesquioxanos organofuncionalizados com tiouréia (T8-Pr-TU), 2,2'-dipiridilamina (T8-Pr-DPA) e 2-Amino-1,3,4-Tiadiazol (T8-Pr-ATD). Os materiais foram caracterizados por: espectroscopia na região do infravermelho (FTIR), ressonância magnética nuclear 29Si e 13C no estado sólido (RMN) e análise elementar. Nos estudos de batelada para os materiais, foram utilizados os íons metálicos de Cd (II), Cu (II), Ni (II) e Co (II) e os solventes foram água e etanol. Determinou-se a dose de adsorvente na solução e o tempo de equilíbrio, na qual, para o material T8-Pr-TU em todos os meios e metais, a capacidade máxima de adsorção ocorreu em 50 mg de adsorvente, e o equilíbrio de adsorção foi de aproximadamente 9 minutos para todos os solventes e íons metálicos, enquanto que, para o T8-Pr-DPA em todos os meios e metais, a capacidade máxima de adsorção ocorreu com 10 mg de adsorvente e tempo de equilíbrio de 10 minutos; já para o T8-Pr-ATD, independentemente do solvente e dos metais, a capacidade máxima de adsorção foi em 50 mg de adsorvente e tempo de equilíbrio de 10 minutos. Estudou-se ainda a capacidade máxima de adsorção (Nf) para os solventes, na qual a capacidade máxima se deu em meio etanólico > aquoso. O efeito dos contra-íons Cl-, Br- e ClO4- foi estudado para todos os materiais, na qual observou-se que para os três adsorventes a capacidade de adsorção seguiu a seguinte ordem: Cl- > Br- > ClO4-. Em seguida, as isotermas de adsorção foram ajustadas pelos modelos Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Para cinética de adsorção dos metais, foram usados três modelos cinéticos como pseudo-primeira-ordem, pseudo-segunda-ordem e Elovich. Os modelos de Langmuir e Elovich foram os mais apropriados para descrever os dados... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: This work describes the synthesis and characterization of silsesquioxanes organofuncionalizados with thiourea (T8-Pr-TU), 2,2 '-dipyridylamine (T8-Pr-DPA) and 2-Amino-1,3,4-thiadiazole (T8-Pr-ATD). The materials were characterized by infrared spectroscopy (FTIR), nuclear magnetic resonance 29Si and 13C solid state (NMR) and elemental analysis. In studies to batch materials were used for metal ions of Cd (II), Cu (II), Ni (II) and Co (II) and the solvents were water and ethanol. It was determined the dose of adsorbent in the solution and equilibrium time in which, for the material T8-Pr-TU in all ways and metals, the maximum adsorption capacity observed in 50 mg of adsorbent, and adsorption equilibrium was about 9 minutes for all metal ions and solvents, whereas for T8-Pr-DPA in all ways and metals, the maximum adsorption capacity was 10 mg of adsorbent and equilibration time of 10 minutes, whereas for T8-Pr-DPA, regardless of solvent and metals, the maximum adsorption capacity was 50 mg of adsorbent and equilibration time of 10 minutes. It was also studied the maximum adsorption capacity (Nf) for solvents, in which the maximum capacity was in ethanolic > aqueous. The effect of the counter ions Cl-, Br-and ClO4- was studied for all materials in which it was observed that the three adsorbents for the adsorption capacity followed the order: Cl-> Br-> ClO4-. Then the adsorption isotherm models were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (DR). For adsorption kinetics of metals, three kinetic models were used as pseudo-first-order, pseudo-second-order and Elovich. The Langmuir model and Elovich were most suitable to describe the data and kinetics of adsorption, respectively, of all materials. From the model isotherm DR, one can calculate the free energy (E)... (Complete abstract click electronic access below)
Mestre

For the selective separation of Noble Metals, different new chelating polymers with the same functional group, based on tri-isobutylphosphine sulphide, have been synthesised. Different spacers between the polymeric matrix and the functional group were introduced during the synthetic process, varying the length and number of heteroatoms (O, S) in the spacer molecule. These polymers show a good affinity towards gold and silver ions and a lower adsorption capacity towards palladium, and do not adsorb all other noble and base metals tested
Nuevos polímeros quelatantes con el mismo grupo funcional, basado en el sulfuro de tri-isobutilfosfina, han sido sintetizados para la separación selectiva de los Metales Nobles. Se han introducido diferentes espaciadores entre la matriz polimérica y los grupos funcionales, variando su longitud y el número de heteroátomos (O, S) presentes. Estos polímeros muestran una buena afinidad para los iones oro y plata, y una capacidad de adsorción inferior para los iones paladio, mientras que no adsorben al resto de Metales Nobles y metales base evaluados
Nous polímers quelatants amb el mateix grup funcional, basat en el sulfur de tri-isobutilfosfina, han estat sintetitzats per a la separació selectiva dels Metalls Nobles. S’han introduit diferents espaiadors entre la matriu polimèrica i els grups funcionals, variant la seva longitud i el nombre d’heteroàtoms (O, S) presents. Aquests polímers mostren una bona afinitat per als ions or i plata, i una capacitat d’adsorció inferior per als ions paladi, mentre que no adsorbeixen la resta de Metalls Nobles i metalls base avaluats

Els carburs de metalls de transició (TMC) exhibeixen propietats químiques i catalítiques similars a les dels costosos metalls nobles. La conversió d'alcohol, hidrogenació d'olefines i altres reaccions importants han demostrat l'aplicabilitat d'aquests compostos en processos industrials. També se sap que nanopartícules de metalls nobles (NMNPs) mostren una alta activitat catalítica tot i la baixa o nul • la reactivitat del metall sòlid. A més, investigacions recents assenyalen que els suports de TMC polaritzen la densitat electrònica de NMNPs adsorbits i augmenten l'activitat catalítica respecte als suports més tradicionals d'òxid metàl • lic. Aquests descobriments recents han inspirat el treball presentat en aquesta tesi, realitzat mitjançant tècniques actuals de la química quàntica. S'ha estudiat CO, CO2, H2, H2O adsorbits sobre TiC i sobre petits clústers d'or adsorbits en el suport. S'ha considerat la superfície (001), terrasses, esglaons monoatòmics i defectes, i també la reactivitat de les molècules adsorbides sobre la superfície neta de TiC (001) i en dos clústers d'or, Au4 i Au6, adsorbits. Les barreres energètiques calculades per a la formació de metà o formaldehid a partir de gas de síntesi, en TiC (001) resulten ser massa altes i aquests processos són inviables sobre el suport net. Sobre els clústers d'or suportats sobre TiC (001) hi ha una major activitat catalítica, però la reacció continua sent altament impedida. No obstant això, la reacció de desplaçament del gas d'aigua es preveu que sigui ràpida en el sistema Au4/TiC (001), superant els catalitzadors utilitzats normalment en la indústria. Experiments recents mostren que els clústers de Ni, Cu i Au estan fortament deformats un cop adsorbits sobre TMC, donant lloc a catalitzadors molt actius. S'ha investigat la interacció dels àtoms amb la fase delta de MoC. La interacció és més forta pel recobriment més baix considerat, la relaxació de la superfície és important i l'activitat es preveu que augmenti en l'ordre Ni> Cu> Au. Finalment, s'han considerat possibles reconstruccions no polars per a la superfície (001) de Mo2C centrant-se en l'energia d’escissió, la qual és proporcional a l'estabilitat de cada tipus de terminació. Les reconstruccions no polars disminueixen l'energia d’escissió, confirmant l'aplicabilitat dels conceptes clàssics de Tasker per a òxids als TMC.
Los carburos de metales de transición (TMC) exhiben propiedades químicas y catalíticas similares a las de los costosos metales nobles. La conversión de alcohol, hidrogenación de olefinas y otras reacciones importantes han demostrado la aplicabilidad de estos compuestos en procesos industriales. También se sabe que nanopartículas de metales nobles (NMNPs) muestran una alta actividad catalítica a pesar de la baja o nula reactividad del metal sólido. Además, investigaciones recientes señalan que los soportes de TMC polarizan la densidad electrónica de NMNPs adsorbidos y aumentan la actividad catalítica respecto a los soportes más tradicionales de óxido metálico. Estos descubrimientos recientes han inspirado el trabajo presentado en esta tesis, realizado mediante técnicas actuales de la química cuántica. Se ha estudiado CO, CO2, H2, H2O adsorbidos sobre TiC y sobre pequeños clusters de oro adsorbidos sobre el suport. Se ha considerado la superficie (001), terrazas, escalones monoatómicos y defectos y, también, la reactividad de las moléculas adsorbidas sobre la superficie limpia de TiC (001) y en dos clusters de oro, Au4 y Au6, adsorbidos. Las barreras energéticas calculadas para la formación de metano o formaldehído a partir de gas de síntesis en la superficie limpia de TiC (001) resultan ser demasiado altas y esos procesos son inviables sobre el soporte limpio. Sobre los clusters de oro soportados sobre TiC (001) hay una mayor actividad catalítica, pero la reacción continúa siendo altamente impedida. Sin embargo la reacción de desplazamiento del gas de agua se prevé que sea rápida en el sistema Au4/TiC (001), superando los catalizadores utilizados normalmente en la industria. Experimentos recientes muestran que los clusters de Ni, Cu y Au están fuertemente deformados una vez adsorbidos sobre TMC dando lugar en catalizadores muy activos. Se ha investigado la interacción de los átomos con la fase delta del catalizador de MoC. La interacción es más fuerte para el recubrimiento más bajo considerado, la relajación de la superficie es importante y la actividad se prevé que aumente en el orden Ni> Cu> Au. Finalmente, se han considerado posibles reconstrucciones no polares para la superficie (001) de Mo2C centrándose en la energía de escisión, que es proporcional a la estabilidad de cada tipo de terminación. Las reconstrucciones no polares disminuyen la energía de escisión, confirmando la aplicabilidad de los conceptos clásicos de Tasker para óxidos a los TMC.
Carbides of the early transition metals (TMC) exhibit chemical and catalytic properties that in many aspects are very similar to those of expensive noble metals. Alcohol conversion, hydrogenation of olefins and many others important reactions demonstrated the applicability of these compounds for industrial processes. It is also known that small noble metal nanoparticles (NMNPs) show high catalytic activity despite of the poor reactivity or inertness of the bulk metal. Additionally, recent investigations pointed out that supporting TMCs polarize the electron density of adsorbed NMNPs increasing the catalytic activity respect to more traditional metal oxide supports. These recent discoveries inspired the work reported in this thesis using state-of-the-art quantum chemical techniques. We studied CO, CO2, H2, H2O molecules adsorbed on TiC and on small gold clusters adsorbed thereon. We considered the (001) extended surface, terraces, monatomic steps and kink defective sites. The reactivity of adsorbed molecules on the clean TiC (001) surface and on two gold clusters, Au4 and Au6, adsorbed thereon were also studied. Energy barriers calculated for methane or formaldehyde formation from syngas, on the clean TiC (001) surface were by far too high and those processes are unviable on the clean support. Gold clusters supported by TiC (001) show higher catalytic activity but the reaction continues to be highly hindered. However water gas shift reaction is predicted to be fast on the Au4/TiC(001) system, overtaking catalysts normally used in industry. Recent experiments show that Ni, Cu and Au clusters are strongly perturbed upon adsorption on TMC resulting in extremely active catalysts. We investigated the interaction of those atoms with the delta phase of the MoC catalyst. The interaction is stronger for the lowest coverage considered, the relaxation of the surface important and the activity is predicted to increase in the order Ni>Cu >Au. Finally, we have studied possible non-polar reconstructions of the (001) surface of Mo2C focusing on the cleavage energy, proportional to the stability of each type of termination. The non-polar reconstructions decreased the calculated cleavage energy, confirming the applicability of the classical Tasker’s concepts for oxides to TMCs.