Caracterização de biomassa lignocelulósica para uso em processos térmicos de geração de energia

Pós-graduação em Química - IQ

Efeito da aplicação do fluido de corte na usinagem da superliga Nimonic 80A

The nickel alloys have a chemical composition with high tenor of alloy elements which are responsible for the material's mechanical and thermal properties, but also are the main causative of problems during the machining, making the process difficult. The objective of this work is the study of the machining by external cylindrical turning of the nickel based alloy Nimonic 80A, seeking the machining optimization of this alloy, seeking the best condition of lubricant fluid use, providing real increases of productivity without the need of investments in new production means. Besides, the results of this work should offer more detailed information regarding the behavior of this alloy in relation to machining by turning. The machining experiences were accomplished in a specimen of the nickel alloy, considering the machining parameters: cutting speed (75 and 90 m/min), cutting depth (0,8 mm) and feed rate (0,15 and 0,18 mm/v). The valuations were accomplished in a CNC lathe and tools with of hard metal inserts. After each stage of the turning the measures of the cutting length were accomplished, of the waste of the tools through a magnifying glass (8x) and the roughness of the specimen evaluated in each phase of the process, with the aid of a portable roughness meter. Through light optical microscopy it was possible to observe the wear of the cutting tools for each appraised condition. The roughness values, Ra and Ry, for the appraised conditions were always superiors to the theoretical values. After analysis of the results it was possible to end that, the best acting for this work strip tested it was obtained for ap=0,8mm: f=0,15mm/rev and VC=75m/min, what resulted in a larger cutting length (1811 m)

Análise proteômica da levedura Saccharomyces cerevisiae CAT-1 cultivada em diferentes concentrações de sacarose

Pós-graduação em Biotecnologia - IQ

Analysis on the formation of a FRC by flux measurements and MHD simulations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Monte Carlo simulation of water-tetrahydrofuran mixtures

Monte Carlo simulations of water-tetrahydrofuran (THF) mixtures were performed in the isothermal-isobaric ensemble (NPT) at T = 298 K and p = 1 atm. The interaction energy was calculated using the TIP4P model for water and a five-site united atom representation for the THF molecule. The potential energy surfaces for water-THF interactions were obtained by using combining rules and the original potential functions used for pure liquids. Theoretical values obtained for the average interaction energy as a function of concentration are in good agreement with available experimental data. Results from the partitioning of the total interaction energy into water-water, water-THF and THF-THF contributions are presented. These results are useful to distinguish between the quantitative contributions of these molecular interactions to the energetic behavior of the water-THF mixing process. The radial distribution functions for HW-OTHF and OW-OTHF site-site interactions show the salient features of hydrogen-bonded liquids. Comparison of the average number of water-water complexes interacting through hydrogen bonding in water-THF and water-methanol mixtures shows an enhancement of the water-water coordination number in a THF rich environment. © 1995.

Caracterização de Filmes a-C:H:Cl e a-C:H:Si:Cl produzidos por deposição à vapor químico assistido por plasma (PECVD) e deposição e implantação iônica por imersão em plasma (PIIID)

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Nonlinear optical characterizations of dibenzoylmethane in solution

This work reports on the two-photon absorption (2PA) cross-section and first hyperpolarizability of dibenzoylmethane solutions using femtosecond Z-scan and hyper-Rayleigh scattering techniques. The 2PA spectrum, spanning the wavelength range from 460 to 740 nm, presents a band centered at 510 nm, with a cross-section value estimated as 37 GM at this wavelength. Owing to the molecular symmetry, this band is not observed in the linear absorption spectrum. The sum-over-state approach was adopted to evaluate various spectroscopic parameters. Experimental and theoretical values of the first hyperpolarizability values were estimated in ethanol and DMSO solutions.

Structural and vibrational study of 8-hydroxyquinoline-2-carboxaldehyde isonicotinoyl hydrazone: a potential metal-protein attenuating compound (MPAC) for the treatment of Alzheimer's disease

A comprehensive structural and vibrational study of the potential metal-protein attenuating compound 8-hydroxyquinoline-2-carboxaldehyde isonicotinoyl hydrazone is reported. X-ray diffraction data, as well as FT-IR and Raman frequencies, were compared with the respective theoretical values obtained from DFT calculations. Theory agrees well with experiment. In this context, an attempt of total assignment concerning the FT-IR and Raman spectra of the title compound was performed, shedding new light on previous partial assignments published elsewhere.

Labile Fe(II) concentrations in the Atlantic sector of the Southern Ocean along a transect from the subtropical domain to the Weddell Sea Gyre

[EN]Labile Fe(II) distributions were investigated in the Sub-Tropical South Atlantic and the Southern Ocean during the BONUS-GoodHope cruise from 34 to 57_ S (February? March 2008). Concentrations ranged from below the detection limit (0.009 nM) to values as high 5 as 0.125 nM. In the surface mixed layer, labile Fe(II) concentrations were always higher than the detection limit, with values higher than 0.060nM south of 47_ S, representing between 39% and 63% of dissolved Fe (DFe). Biological production was evidenced. At intermediate depth, local maxima were observed, with the highest values in the Sub-Tropical domain at around 200 m, and represented more than 70% of DFe. Remineralization processes were likely responsible for those sub-surface maxima. Below 1500 m, concentrations were close to or below the detection limit, except at two stations (at the vicinity of the Agulhas ridge and in the north of the Weddell Sea Gyre) where values remained as high as _0.030?0.050 nM. Hydrothermal or sediment inputs may provide Fe(II) to these deep waters. Fe(II) half life times (t1/2) at 4 _C were measured in the upper and deep waters and ranged from 2.9 to 11.3min, and from 10.0 to 72.3 min, respectively. Measured values compared quite well in the upper waters with theoretical values from two published models, but not in the deep waters. This may be due to the lack of knowledge for some parameters in the models and/or to organic complexation of Fe(II) that impact its oxidation rates. This study helped to considerably increase the Fe(II) data set in the Ocean and to better understand the Fe redox cycle.

Untersuchungen an gespeicherten 40 Ca +-Ionen in einer linearen Paulfalle

In Experimenten an lasergekühlten, in einer linearen Paulfalle gespeicherten $Ca^+$-Ionen wurde dieLebensdauer des metastabilen $3D_{5/2}$-Niveaus durch Beobachtung von Quantensprüngen einzelner Ionen zu 1100(18)msbestimmt. Systematische Fehler durch quenchende Stöße oder Stark-Mischen durch das Speicherfeld liegen unterhalb dererreichten Genauigkeit. Abweichungen von früheren Messungen konnten durch eine vernachlässigte Abhängigkeit derLebensdauer von der Laserleistung des Rückpumplasers erklärt werden. Das Endergebnis zeigt gute Übereinstimmung mitneueren theoretischen Werten. In weiteren Messungen an zehn Ionen wurde in einigen Messreihen eine deutliche Reduktionder Lebensdauer gegenüber einem einzelnen Ion festgestellt. Dabei wurden mehr koinzidente Zerfälle von zwei und dreiIonen beobachtet als für unabhängige Teilchen zu erwarten. In einem Ionenkristall wurde eine räumliche Trennung atomarer Zustände erreicht. Dabei wurde ein Teil der Ionen einesKristalls aus einigen hundert Ionen in den metastabilen Zustand gepumpt, der von den Kühllasern vollständig entkoppeltist. Durch sympathetische Kühlung werden diese Ionen weiterhin gekühlt und der Kristall schmilzt nicht. Durch denLichtdruck, den die Kühllaser ausgeüben, werden die Ionen nach atomaren Zuständen sortiert, weil die lasergekühltenIonen einen Rückstoß erfahren, die übrigen aber nicht. Für zukünftige Experimente wurden Verbesserungen des experimentellen Aufbaus auf den Weg gebracht. So wurden Methodenund Komponenten für eine verbesserte Frequenzstabilisierung der Diodenlaser entwickelt.

Magnetic properties of selected 3d- and 4f-systems on alpha-Al 2 O 3 substrates

In this work the growth and the magnetic properties of the transition metals molybdenum, niobium, and iron and of the highly-magnetostrictive C15 Laves phases of the RFe2 compounds (R: Rare earth metals: here Tb, Dy, and Tb{0.3}Dy{0.7} deposited on alpha-Al2O3 (sapphire) substrates are analyzed. Next to (11-20) (a-plane) oriented sapphire substrates mainly (10-10) (m-plane) oriented substrates were used. These show a pronounced facetting after high temperature annealing in air. Atomic force microscopy (AFM) measurements reveal a dependence of the height, width, and angle of the facets with the annealing temperature. The observed deviations of the facet angles with respect to the theoretical values of the sapphire (10-1-2) and (10-11) surfaces are explained by cross section high resolution transmission electron microscopy (HR-TEM) measurements. These show the plain formation of the (10-11) surface while the second, energy reduced (10-1-2) facet has a curved shape given by atomic steps of (10-1-2) layers and is formed completely solely at the facet ridges and valleys. Thin films of Mo and Nb, respectively, deposited by means of molecular beam epitaxy (MBE) reveal a non-twinned, (211)-oriented epitaxial growth as well on non-faceted as on faceted sapphire m-plane, as was shown by X-Ray and TEM evaluations. In the case of faceted sapphire the two bcc crystals overgrow the facets homogeneously. Here, the bcc (111) surface is nearly parallel to the sapphire (10-11) facet and the Mo/Nb (100) surface is nearly parallel to the sapphire (10-1-2) surface. (211)-oriented Nb templates on sapphire m-plane can be used for the non-twinned, (211)-oriented growth of RFe2 films by means of MBE. Again, the quality of the RFe2 films grown on faceted sapphire is almost equal to films on the non-faceted substrate. For comparison thin RFe2 films of the established (110) and (111) orientation were prepared. Magnetic and magnetoelastic measurements performed in a self designed setup reveal a high quality of the samples. No difference between samples with undulated and flat morphology can be observed. In addition to the preparation of covering, undulating thin films on faceted sapphire m-plane nanoscopic structures of Nb and Fe were prepared by shallow incidence MBE. The formation of the nanostructures can be explained by a shadowing of the atomic beam due to the facets in addition to de-wetting effects of the metals on the heated sapphire surface. Accordingly, the nanostructures form at the facet ridges and overgrow them. The morphology of the structures can be varied by deposition conditions as was shown for Fe. The shape of the structures vary from pearl-necklet strung spherical nanodots with a diameter of a few 10 nm to oval nanodots of a few 100 nm length to continuous nanowires. Magnetization measurements reveal uniaxial magnetic anisotropy with the easy axis of magnetization parallel to the facet ridges. The shape of the hysteresis is depending on the morphology of the structures. The magnetization reversal processes of the spherical and oval nanodots were simulated by micromagnetic modelling and can be explained by the formation of magnetic vortices.

Investigation Of Leucine And Glutamic Acid Properties From The Nanoscale To The Macroscale

Aerosols are known to have important effects on climate, the atmosphere, and human health. The extent of those effects is unknown and largely depend on the interaction of aerosols with water in the atmosphere. Ambient aerosols are complex mixtures of both inorganic and organic compounds. The cloud condensation nuclei (CCN) activities, hygroscopic behavior and particle morphology of a monocarboxylic amino acid (leucine) and a dicarboxylic amino acid (glutamic acid) were investigated. Activation diameters at various supersaturation conditions were experimentally determined and compared with Köhler theoretical values. The theory accounts for both surface tension and the limited solubility of organic compounds. It was discovered that glutamic acid aerosols readily took on water both when relative humidity was less than 100% and when the supersaturation condition was reached, while leucine did not show any water activation at those conditions. Moreover, the study also suggests that Köhler theory describes CCN activity of organic compounds well when only surface tension of the compound is taken into account and complete solubility is assumed. Single parameter ¿ was also computed using both CCN data and hygroscopic growth factor (GF). The results of ¿ range from 0.17 to 0.53 using CCN data and 0.09 to 0.2 using GFs. Finally, the study suggests that during the water-evaporation/particle-nucleation process, crystallization from solution droplets takes place at different locations: for glutamic acid at the particles¿ center and leucine at the particles¿ boundary.

Price risk management in the copper market using commodity derivatives and options strategies

Metals price risk management is a key issue related to financial risk in metal markets because of uncertainty of commodity price fluctuation, exchange rate, interest rate changes and huge price risk either to metals’ producers or consumers. Thus, it has been taken into account by all participants in metal markets including metals’ producers, consumers, merchants, banks, investment funds, speculators, traders and so on. Managing price risk provides stable income for both metals’ producers and consumers, so it increases the chance that a firm will invest in attractive projects. The purpose of this research is to evaluate risk management strategies in the copper market. The main tools and strategies of price risk management are hedging and other derivatives such as futures contracts, swaps and options contracts. Hedging is a transaction designed to reduce or eliminate price risk. Derivatives are financial instruments, whose returns are derived from other financial instruments and they are commonly used for managing financial risks. Although derivatives have been around in some form for centuries, their growth has accelerated rapidly during the last 20 years. Nowadays, they are widely used by financial institutions, corporations, professional investors, and individuals. This project is focused on the over-the-counter (OTC) market and its products such as exotic options, particularly Asian options. The first part of the project is a description of basic derivatives and risk management strategies. In addition, this part discusses basic concepts of spot and futures (forward) markets, benefits and costs of risk management and risks and rewards of positions in the derivative markets. The second part considers valuations of commodity derivatives. In this part, the options pricing model DerivaGem is applied to Asian call and put options on London Metal Exchange (LME) copper because it is important to understand how Asian options are valued and to compare theoretical values of the options with their market observed values. Predicting future trends of copper prices is important and would be essential to manage market price risk successfully. Therefore, the third part is a discussion about econometric commodity models. Based on this literature review, the fourth part of the project reports the construction and testing of an econometric model designed to forecast the monthly average price of copper on the LME. More specifically, this part aims at showing how LME copper prices can be explained by means of a simultaneous equation structural model (two-stage least squares regression) connecting supply and demand variables. A simultaneous econometric model for the copper industry is built: {█(Q_t^D=e^((-5.0485))∙P_((t-1))^((-0.1868) )∙〖GDP〗_t^((1.7151) )∙e^((0.0158)∙〖IP〗_t ) @Q_t^S=e^((-3.0785))∙P_((t-1))^((0.5960))∙T_t^((0.1408))∙P_(OIL(t))^((-0.1559))∙〖USDI〗_t^((1.2432))∙〖LIBOR〗_((t-6))^((-0.0561))@Q_t^D=Q_t^S )┤ P_((t-1))^CU=e^((-2.5165))∙〖GDP〗_t^((2.1910))∙e^((0.0202)∙〖IP〗_t )∙T_t^((-0.1799))∙P_(OIL(t))^((0.1991))∙〖USDI〗_t^((-1.5881))∙〖LIBOR〗_((t-6))^((0.0717) Where, Q_t^D and Q_t^Sare world demand for and supply of copper at time t respectively. P(t-1) is the lagged price of copper, which is the focus of the analysis in this part. GDPt is world gross domestic product at time t, which represents aggregate economic activity. In addition, industrial production should be considered here, so the global industrial production growth that is noted as IPt is included in the model. Tt is the time variable, which is a useful proxy for technological change. A proxy variable for the cost of energy in producing copper is the price of oil at time t, which is noted as POIL(t ) . USDIt is the U.S. dollar index variable at time t, which is an important variable for explaining the copper supply and copper prices. At last, LIBOR(t-6) is the 6-month lagged 1-year London Inter bank offering rate of interest. Although, the model can be applicable for different base metals' industries, the omitted exogenous variables such as the price of substitute or a combined variable related to the price of substitutes have not been considered in this study. Based on this econometric model and using a Monte-Carlo simulation analysis, the probabilities that the monthly average copper prices in 2006 and 2007 will be greater than specific strike price of an option are defined. The final part evaluates risk management strategies including options strategies, metal swaps and simple options in relation to the simulation results. The basic options strategies such as bull spreads, bear spreads and butterfly spreads, which are created by using both call and put options in 2006 and 2007 are evaluated. Consequently, each risk management strategy in 2006 and 2007 is analyzed based on the day of data and the price prediction model. As a result, applications stemming from this project include valuing Asian options, developing a copper price prediction model, forecasting and planning, and decision making for price risk management in the copper market.

Faulted Structures in Li Ion Exchanged NaMO2 (M=Ni(0.25)Mn(0.75))

A family of LiMO2 materials (M=Ni0.25Mn0.75) was prepared from Na1.2-xLixMO∂ precursors (0≤x≤0.6) via ion exchange. The resulting IE products were examined via XRD and compared to simulated XRD patterns produced using DIFFax to determine the defect structures resulting from the IE process. For the 0.1≤x≤0.6 materials, it is observed that there are 3 LiMO2 sub-phases with different Li contents present. As the amount of Li in the precursor increases, the amount of each phase changes resulting in a net shift to higher 2-theta; corresponding to an overall decrease in lattice parameter, approaching the theoretical values for LiMO2. Additionally, as x increases, the probability of O3-type shifting increases, most likely due to an increase in the amount O3-Li2MO3 minority phase which acts to weaken bonds in the TM layer, allowing the O3 shift to occur more easily. For the x=0 IE product, it was seen that the product had an ~O2-type structure, but with lattice parameters closer to those expected for a NaMO2 material.

Simulation study of joint transition and Weibull survival model with shared parameters

This study investigates a theoretical model where a longitudinal process, that is a stationary Markov-Chain, and a Weibull survival process share a bivariate random effect. Furthermore, a Quality-of-Life adjusted survival is calculated as the weighted sum of survival time. Theoretical values of population mean adjusted survival of the described model are computed numerically. The parameters of the bivariate random effect do significantly affect theoretical values of population mean. Maximum-Likelihood and Bayesian methods are applied on simulated data to estimate the model parameters. Based on the parameter estimates, predicated population mean adjusted survival can then be calculated numerically and compared with the theoretical values. Bayesian method and Maximum-Likelihood method provide parameter estimations and population mean prediction with comparable accuracy; however Bayesian method suffers from poor convergence due to autocorrelation and inter-variable correlation. ^