In this study, molecular dynamics (MD) simulations was employed to investigate (5,5), (10,10) single-walled nanocoils and (5,5)@(10,10) double-walled carbon nanocoils. The study can be arranged into two parts¡G In part I: Investigate the mechanical properties of (5,5), (10,10) single-walled nanocoils and (5,5)@(10,10) double-walled carbon nanocoils. The second reactive empirical bond order (REBO) potential was employed to model the interaction between carbon atoms. The contours of atomic slip vector and sequential slip vector were used to investigate the structural variations at different strains during the tension process. The yielding stress, maximum tensile strength, and Young¡¦s modulus were determined from the tensile stress-strain profiles. The results show that the nanocoils have superelastic characteristics to the carbon nanotube in the same tube diameter. In part II: Investigate the diffusion behavior of water molecules confined inside narrow (5,5) and (10,10) carbon nanocoils under different tensile strains. The condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) potential was employed to model the interaction between carbon-carbon atoms¡Acarbon atoms-water molecules and water-water molecules. To analysis the kinetic behavior of water molecules in two carbon nanocoils, the diffusion coefficients, square displacement (SD) and mean square displacement (MSD) of water molecules were calculated. The results show that diffusion coefficient of water will increase with the strains of carbon nanocoils. However, the diffusion coefficient has a significant decrease in a large strain due to the structural deformation of carbon nanocoils. The diffusion behaviors of water inside the (5,5) and (10,10) carbon nanotubes were also investigated to compare the results in (5,5) and (10,10) carbon nanotubes. Our results indicate that two carbon nanocoils have a lower diffusion coefficient of water than that of carbon nanotubes because the geometry of carbon nanocoil is easily to block up the diffusion of water molecules.

In this dissertation, the molecular behaviors of water/ethanol mixtures of different weight fractions inside Au nanotubes of different radii at steady state were investigated by molecular dynamics simulation. Five weight fractions of water/ethanol (0/100, 100/0, 25/75, 50/50, and 75/25) and three radii of Au nanotubes (13, 22, and 31.1 Å) were considered in order to understand the effects of Au nanotube size and water/ethanol fraction on the structural and dynamical behaviors of the water and ethanol molecules. The density profiles show two shell-like formations inside the Au nanotubes because water molecules prefer to adsorb on the wall of Au nanotube. According to the density distribution, the space inside Au nanotubes can be divided into three regions, those of contact, transition, and bulk regions, in order from the interior wall surface to the nanotube center. The bulk region has a lower local weight fraction compared to the system water/ethanol weight fraction. In addition, the local water/ethanol weight fraction in the contact region is higher than that of the system. When the system water/ethanol weight fraction becomes higher, the local water/ethanol weight fraction also becomes higher. In 25/75, 50/50, and 75/25 weight fraction mixtures, the number of H-bonds per water and per ethanol are different from those of pure 100% water and 100% ethanol in the Au nanotube due to the nanoconfinement effect. Moreover, the distribution of number of H-bonds in regions where there is only one material will be similar to the distribution in the corresponding region of the pure material, whether 100% water or ethanol. In all regions, the probability to form different H-bonds is affected significantly by the local weight fraction of water/ethanol. Three radii of Au nanotubes (13, 22, and 31.1 Å) were considered in order to understand the effects of Au nanotube size and water/ethanol fraction on the structural and dynamical behaviors of the water and ethanol molecules. In the transition and bulk regions, diffusion coefficients for water and ethanol molecules become higher due to the weak interaction with Au atoms. The values of diffusion coefficients for water molecules in the contact regions are much lower than for those in other regions and are similar for different water/ethanol weight fractions due to the strong interaction with Au atoms. When the radius of the Au nanotube becomes larger, the values of local weight fraction inside the larger radius Au nanotube become higher than those inside small radius Au nanotubes because the ratio of water number to the nanotube inner surface area becomes higher. In addition, water inside a larger radius Au nanotube has a shorter water-water hydrogen bond lifetime (H-bond) in the contact region because the smaller curvature causes weaker interaction with Au atoms.

This research evaluated the effectiveness of a commercially available adsorbent, Kemiron, to remove arsenic from conditions representative of landfill leachate. Kemiron was identified as an iron oxide of 39.8 m 2/g surface area, 44 % of which resided in the less than 3 nm pore size range. Batch experiments of As(V) and As(III) were conducted with particle sizes either ≤38 μm and in the range 500 – 600 μm with equilibrium being reached in the smaller particles in ~ 36 hours and estimated at 374 hrs for the larger particles. Ionic strength did not affect the mass loadings of As(V) and As(III) which approached 80 mg/g sorbent and greater than 90 mg/g respectively at pH 7. The effect of Se(IV) and Ni(II) was greater on As(III) than on As(V) sorption with as much as a 40% reduction in As(III) sorption in the presence of a similar amount of Se(IV). Sulfate, calcium and carbonate reduced As(III) sorption whereas calcium enhanced As(V) sorption. As removal tested in synthetic landfill leachate under both young and old landfill conditions indicated that pH, ORP, and Se(IV) as a co-contaminant with 1:1 mg/L concentration to As were the most significant key factors that influence As adsorption. Over 90% of 5 mg/L As(V) as initial concentration was removed at pH 7.2 within an operating range of 197 and 371.6 mV of ORP and 99% removal was also achieved at ~ pH 11 under the range of -335.7 and 9.1 mV of ORP where the latter condition would be unlikely in real leachate. Preliminary experiments with real leachate solutions show similar sorption behavior for As(V) though the total amount removed was reduced. Whilst this work shows the potential for sorption technology as a treatment option for heavy metal removal from landfill leachate, further tests are definitely needed to determine the various pre-treatment options needed before real leachate solutions can be treated. Many commercially available sorbents have been developed for contaminated drinking waters and this is the first study that has looked at their application to the more complex leachate matrix.

One-dimensional ZnO nanostructures have great potential applications in the fields of optoelectronic and sensor devices.  Therefore, it is very important to realize the controllable growth of one-dimensional ZnO nanostructures and investigate their properties. The main points for this thesis are not only to successfully realize the controllable growth of ZnO nanorods (ZNRs), ZnO nanotubes (ZNTs) and ZnMgO/ZnO heterostructures, but also investigate the structure and optical properties in detail by means of scanning electron microscope (SEM), transmission electron microscope (TEM), resonant Raman spectroscopy (RRS), photoluminescence (PL), time resolved PL (TRPL), X-ray photoelectron spectroscopy (XPS) and Secondary ion mass spectrometry (SIMS). For ZNRs, on one hand, ZNRs have been successfully synthesized by a two-step chemical bath deposition method on Si substrates. The diameter of ZNRs can be well controlled from 150 nm to 40 nm through adjusting the diameter and density of the ZnO nanoparticles pretreated on the Si substrates. The experimental results indicated that both diameter and density of ZnO nanoparticles on the substrates determined the diameter of ZNRs. But when the density is higher than the critical value of 2.3×108cm-2, the density will become the dominant factor to determine the diameter of ZNRs. One the other hand, the surface recombination of ZNRs has been investigated in detail. Raman, RRS and PL results help us reveal that the surface defects play a significant role in the as-grown sample. It is the first time to the best of our knowledge that the Raman measurements can be used to monitor the change of surface defects and deep level defects in the CBD grown ZNRs. Then we utilized TRPL technique, for the first time, to investigate the CBD grown ZNRs with different diameters. The results show that the decay time of the excitons in ZNRs strongly depends on the diameter. The altered decay time is mainly due to the surface recombination process. A thermal treatment under 500°C can strongly suppress the surface recombination channel. A simple carrier and exciton diffusion equation is also used to determine the surface recombination velocity, which results in a value between 1.5 and 4.5 nm/ps. Subsequently, we utilized XPS technique to investigate the surface composition of as-grown and annealed ZNRs so that we can identify the surface recombination centers. The experimental results indicated that the OH and H bonds play the dominant role in facilitating surface recombination but specific chemisorbed oxygen also likely affect the surface recombination. Finally, on the basis of results above, we explored an effective way, i.e. sealing the beaker during the growth process, to effectively suppress the surface recombination of ZNRs and the suppression effect is even better than a 500oC post-thermal treatment. For ZNTs, the structural and optical properties have been studied in detail. ZNTs have been successfully evolved from ZNRs by a simple chemical etching process. Both temperature-dependent PL and TRPL results not only further testify the coexistence of spatially indirect and direct transitions due to the surface band bending, but also reveal that less nonradiative contribution to the emission process in ZNTs finally causes their strong enhancement of luminescence intensity. For ZnMgO/ZnO heterostructures, the Zn0.94Mg0.06O/ZnO heterostructures have been deposited on 2 inch sapphire wafer by metal organic chemical vapor deposition (MOCVD) equipment. PL mapping demonstrates that Mg distribution in the entire wafer is quite uniform with average concentration of ~6%. The annealing effects on the Mg diffusion behaviors in Zn0.94Mg0.06O/ZnO heterostructures have been investigated by SIMS in detail. All the SIMS depth profiles of Mg element have been fitted by three Gaussian distribution functions. The Mg diffusion coefficient in the as-grown Zn0.94Mg0.06O layer deposited at 700 oC is two orders of magnitude lower than that of annealing samples, which clearly testifies that the deposited temperature of 700 oC is much more beneficial to grow ZnMgO/ZnO heterostructures or quantum wells. This thesis not only provides the effective way to fabricate ZNRs, ZNTs and ZnMgO/ZnO heterostructures, but also obtains some beneficial results in aspects of their optical properties, which builds theoretical and experimental foundation for much better understanding fundamental physics and broader applications of low-dimensional ZnO and related structures. / Endimensionella nanostrukturer av ZnO har stora potentiella tillämpningar för optoelektroniska komponenter och sensorer. Huvudresultaten för denna avhandling är inte bara att vi framgångsrikt har realiserat med en kontrollerbar metod ZnO nanotrådar (ZNRs), ZnO nanotuber (ZNTs) och ZnMgO/ZnO heterostrukturer, utan vi har också undersökt deras struktur och optiska egenskaper i detalj. För ZNRs har diametern blivit välkontrollerad från 150 nm  ner till 40 nm. Den storlekskontrollerande mekanismen är i huvudsak relaterad till tätheten av ZnO partiklarna som är fördeponerade på substratet. De optiska mätningarna ger upplysning om att ytrekombinationsprocessen spelar en betydande roll för tillväxten av ZNR. En värmebehandling i efterhand  vid 500 grader Celsius eller användande av en förseglad glasbägare under tillväxtprocessen kan starkt hålla nere kanalerna för ytrekombinationen.För ZNT, dokumenterar vi inte bara samexistensen av rumsliga indirekta och direkta  övergångar på grund av bandböjning, men vi konstaterar också att vi har mindre icke-strålande bidrag till den optiska emissionsprocessen i ZNT. För ZnMgO/ZnO heterostrukturer konstaterar vi med hjälp av analys av Mg diffusionen i den växta och den i efterhand uppvärmda Zn(0.94)Mg(0.06)O filmen, att en tillväxt vid 700 grader Celsius är den mest lämpliga för att växa ZnMgO/ZnO heterostrukturer eller kvantbrunnar.   Denna avhandling ger en teoretisk och experimentell grund för bättre förståelse av grundläggande fysik och för tillämpningar av lågdimensionella strukturer. / SSF, VR

Acid treatments have predominantly been conducted using HCl for its availability, high rock dissolving power and soluble reaction products. At high temperatures, rapid spending of the acid with carbonates prevents deeper penetration distance into the formations. Alternative fluids such as acetic and formic acid have lent themselves to retarded reaction rates, low corrosivity and reduced tendency to form acid/oil sludge in asphaltene-rich crudes but for high reaction rate problems. Chelating agents, with the added advantage of complexing with alkali-earth metals in carbonates to form water-soluble products that are thermally stable at high temperature, have been introduced as stimulation fluids. Glutamic acid diacetic acid (GLDA) ethylenediaminetetraacetic acid (EDTA) and hydroxyethylenediaminetriacetic acid (HEDTA) are aminopolycarboxylic acids that were studied. To predict the spending of chelating agents relative to simple organic acids at temperatures between 150 and 250˚F, the chemical kinetics of dolomite dissolution in these acid solutions were investigated over different reaction conditions in a rotating disk apparatus. Samples of the reacted acids from the reactor were collected and then analyzed with inductively coupled plasma (ICP). Analyses of the experimental data were carried out to determine kinetic parameters of the heterogeneous reactions needed for matrix stimulation of dolomitic reservoirs. Experimental results indicated that dolomite dissolution rates increased in all the acid solutions as the disk rotational speeds increased at 150, 200, and 250˚F. The dissolution of dolomite in 0.886 M GLDA was found to be surface-reaction limited at lower temperatures and mass-transfer limited at highest temperature. GLDA with the lowest reaction rates and relative diffusion coefficient demonstrated retardation before spending with deeper penetration capability for productivity and injectivity improvement.

O soro de queijo, um subproduto industrial altamente poluidor, constitui-se em um substrato rico em nutrientes e de grande potencial de aproveitamento em bioprocessos. A utilização de substratos alternativos e de baixo custo para a produção de etanol, tais como resíduos industriais, vem sendo recentemente estudada, com resultados promissores. Diante deste contexto, o presente trabalho teve como objetivo otimizar a bioconversão do soro de queijo em etanol em biorreatores imobilizados usando Kluyveromyces marxianus como biocatalisador e avaliar as limitações de transferência de massa em esferas de alginato de cálcio mediante o cálculo do coeficiente de difusão. Valores similares do fator de conversão da lactose em etanol, YEtOH/S, (0,44±0,01 g g -1) foram encontrados ao testar a produção do etanol por três linhagens de K. marxianus (CBS 6556, CCT 4086 e CCT 2653) em biorreator de leito fluidizado em regime batelada, e uma diminuição na eficiência de conversão (83,3- 66,1%) e na produtividade volumétrica (0,96 a 0,78 g L-1h-1) foi observada ao aumentar a temperatura de fermentação (30-40ºC) utilizando K. marxianus CBS 6556 imobilizada. Em seguida, foram testados biorreatores de leito fixo e fluidizado operados continuamente por diferentes taxas de diluição (0,1-0,3 h-1). Os valores indicaram que o aumento da taxa de diluição leva a um decréscimo da utilização de lactose e da produção de etanol e um aumento da produtividade volumétrica (QP). Valores semelhantes do fator de conversão de lactose em etanol (YEtOH/S) foram encontrados para todas as taxas de diluição testadas, em ambos sistemas de biorreator (fixo e fluidizado). A maior produtividade volumétrica foi obtida para a taxa de diluição de 0,3 h-1 em biorreator de leito fluidizado, alcançando 87% da conversão teórica, e a maior concentração de etanol (27,9 g L-1) foi obtida com a taxa de diluição de 0,1 h-1. As imagens de microscopia eletrônica de varredura (MEV) na superfície das esferas mostraram que a imobilização em alginato de cálcio foi eficaz. O estudo da transferência de massa da lactose e do etanol em esferas de cálcio foi realizado através da medição do coeficiente de difusão com base na abordagem matemática da Segunda Lei de Fick. Diferentes condições experimentais foram testadas. Os resultados obtidos mostraram que o coeficiente de difusão independe da concentração da solução de lactose (25, 50 e 75 g L-1) e de etanol (25 e 50 g L- 1), bem como da concentração de alginato (3, 4 e 6%), e que é afetado pela temperatura (25, 30 e 35 ºC), aumentando de 4,67×10-10 m2 s-1 a 6,96×10-10 m2 s-1 para a lactose, e de 1,46×10-10 m2 s-1 a 2,68×10-10 m2 s-1 para o etanol. / Cheese whey, an industrial by-product with highly pollutant characteristics, is a substrate for cell growth, rich in nutrients and with great potential for use in bioprocesses. The utilization of alternative and low cost substrates for the production of ethanol, such as industrial waste, has been recently studied with promising results. In this context, the aim of this work was to optimize the bioconversion of cheese whey into ethanol in bioreactors using immobilized Kluyveromyces marxianus as biocatalyst and evaluate the mass transfer limitations in Ca-alginate beads by measuring the diffusion coefficient. Similar ethanol yields (0.44±0.01 g EtOH g sugar-1) were found when testing the ethanol production by three strains of K. marxianus (CBS 6556, CCT 4086 and CCT 2653) in batch fluidized bed bioreactor, a decrease in conversion efficiency (83.3 to 66.1%) and ethanol productivity (0.96 to 0.78 g L- 1.h-1) was observed with the increase of fermentation temperature (30-40ºC) by immobilized K. marxianus CBS 6556. Continuous fluidized and packed bed bioreactors with different dilution rates (0.1 to 0.3 h-1) were performed. Values indicated that the increase of dilution rate led to a decrease in lactose utilization and ethanol production and an increase in ethanol productivity (QP). Similar ethanol yields (YEtOH/S) were obtained for all dilution rates tested, in both bioreactor systems. The highest ethanol productivity (3.5 g L-1h-1) was obtained at dilution rate of 0.3 h-1 in the fluidized bed bioreactor, with 87% of the theoretical conversion. The highest ethanol concentration (27.9 g L-1) was obtained at dilution rate of 0.1 h-1. The SEM micrographies of beads demonstrated that the cell immobilization in the Ca-alginate was effective. Lactose and ethanol mass transfer studies in Ca-alginate beads was performed by measuring the diffusion coefficient based on the mathematical approach of the Fick’s second Law. Different experimental conditions were tested. Results showed that diffusion coefficients were independent from the concentration of lactose (25, 50 and 75 g L-1) and ethanol (25 and 50 g L-1), as well as from the concentration of Ca-alginate (3, 4 and 6%), but were affected by temperature, increasing from 4.67×10-10 m2 s-1 to 6.96×10-10 m2 s-1 for lactose, and from 1.46×10-10 m2 s-1 to 2.68×10-10 m2 s-1 for ethanol.

O soro de queijo, um subproduto industrial altamente poluidor, constitui-se em um substrato rico em nutrientes e de grande potencial de aproveitamento em bioprocessos. A utilização de substratos alternativos e de baixo custo para a produção de etanol, tais como resíduos industriais, vem sendo recentemente estudada, com resultados promissores. Diante deste contexto, o presente trabalho teve como objetivo otimizar a bioconversão do soro de queijo em etanol em biorreatores imobilizados usando Kluyveromyces marxianus como biocatalisador e avaliar as limitações de transferência de massa em esferas de alginato de cálcio mediante o cálculo do coeficiente de difusão. Valores similares do fator de conversão da lactose em etanol, YEtOH/S, (0,44±0,01 g g -1) foram encontrados ao testar a produção do etanol por três linhagens de K. marxianus (CBS 6556, CCT 4086 e CCT 2653) em biorreator de leito fluidizado em regime batelada, e uma diminuição na eficiência de conversão (83,3- 66,1%) e na produtividade volumétrica (0,96 a 0,78 g L-1h-1) foi observada ao aumentar a temperatura de fermentação (30-40ºC) utilizando K. marxianus CBS 6556 imobilizada. Em seguida, foram testados biorreatores de leito fixo e fluidizado operados continuamente por diferentes taxas de diluição (0,1-0,3 h-1). Os valores indicaram que o aumento da taxa de diluição leva a um decréscimo da utilização de lactose e da produção de etanol e um aumento da produtividade volumétrica (QP). Valores semelhantes do fator de conversão de lactose em etanol (YEtOH/S) foram encontrados para todas as taxas de diluição testadas, em ambos sistemas de biorreator (fixo e fluidizado). A maior produtividade volumétrica foi obtida para a taxa de diluição de 0,3 h-1 em biorreator de leito fluidizado, alcançando 87% da conversão teórica, e a maior concentração de etanol (27,9 g L-1) foi obtida com a taxa de diluição de 0,1 h-1. As imagens de microscopia eletrônica de varredura (MEV) na superfície das esferas mostraram que a imobilização em alginato de cálcio foi eficaz. O estudo da transferência de massa da lactose e do etanol em esferas de cálcio foi realizado através da medição do coeficiente de difusão com base na abordagem matemática da Segunda Lei de Fick. Diferentes condições experimentais foram testadas. Os resultados obtidos mostraram que o coeficiente de difusão independe da concentração da solução de lactose (25, 50 e 75 g L-1) e de etanol (25 e 50 g L- 1), bem como da concentração de alginato (3, 4 e 6%), e que é afetado pela temperatura (25, 30 e 35 ºC), aumentando de 4,67×10-10 m2 s-1 a 6,96×10-10 m2 s-1 para a lactose, e de 1,46×10-10 m2 s-1 a 2,68×10-10 m2 s-1 para o etanol. / Cheese whey, an industrial by-product with highly pollutant characteristics, is a substrate for cell growth, rich in nutrients and with great potential for use in bioprocesses. The utilization of alternative and low cost substrates for the production of ethanol, such as industrial waste, has been recently studied with promising results. In this context, the aim of this work was to optimize the bioconversion of cheese whey into ethanol in bioreactors using immobilized Kluyveromyces marxianus as biocatalyst and evaluate the mass transfer limitations in Ca-alginate beads by measuring the diffusion coefficient. Similar ethanol yields (0.44±0.01 g EtOH g sugar-1) were found when testing the ethanol production by three strains of K. marxianus (CBS 6556, CCT 4086 and CCT 2653) in batch fluidized bed bioreactor, a decrease in conversion efficiency (83.3 to 66.1%) and ethanol productivity (0.96 to 0.78 g L- 1.h-1) was observed with the increase of fermentation temperature (30-40ºC) by immobilized K. marxianus CBS 6556. Continuous fluidized and packed bed bioreactors with different dilution rates (0.1 to 0.3 h-1) were performed. Values indicated that the increase of dilution rate led to a decrease in lactose utilization and ethanol production and an increase in ethanol productivity (QP). Similar ethanol yields (YEtOH/S) were obtained for all dilution rates tested, in both bioreactor systems. The highest ethanol productivity (3.5 g L-1h-1) was obtained at dilution rate of 0.3 h-1 in the fluidized bed bioreactor, with 87% of the theoretical conversion. The highest ethanol concentration (27.9 g L-1) was obtained at dilution rate of 0.1 h-1. The SEM micrographies of beads demonstrated that the cell immobilization in the Ca-alginate was effective. Lactose and ethanol mass transfer studies in Ca-alginate beads was performed by measuring the diffusion coefficient based on the mathematical approach of the Fick’s second Law. Different experimental conditions were tested. Results showed that diffusion coefficients were independent from the concentration of lactose (25, 50 and 75 g L-1) and ethanol (25 and 50 g L-1), as well as from the concentration of Ca-alginate (3, 4 and 6%), but were affected by temperature, increasing from 4.67×10-10 m2 s-1 to 6.96×10-10 m2 s-1 for lactose, and from 1.46×10-10 m2 s-1 to 2.68×10-10 m2 s-1 for ethanol.

O soro de queijo, um subproduto industrial altamente poluidor, constitui-se em um substrato rico em nutrientes e de grande potencial de aproveitamento em bioprocessos. A utilização de substratos alternativos e de baixo custo para a produção de etanol, tais como resíduos industriais, vem sendo recentemente estudada, com resultados promissores. Diante deste contexto, o presente trabalho teve como objetivo otimizar a bioconversão do soro de queijo em etanol em biorreatores imobilizados usando Kluyveromyces marxianus como biocatalisador e avaliar as limitações de transferência de massa em esferas de alginato de cálcio mediante o cálculo do coeficiente de difusão. Valores similares do fator de conversão da lactose em etanol, YEtOH/S, (0,44±0,01 g g -1) foram encontrados ao testar a produção do etanol por três linhagens de K. marxianus (CBS 6556, CCT 4086 e CCT 2653) em biorreator de leito fluidizado em regime batelada, e uma diminuição na eficiência de conversão (83,3- 66,1%) e na produtividade volumétrica (0,96 a 0,78 g L-1h-1) foi observada ao aumentar a temperatura de fermentação (30-40ºC) utilizando K. marxianus CBS 6556 imobilizada. Em seguida, foram testados biorreatores de leito fixo e fluidizado operados continuamente por diferentes taxas de diluição (0,1-0,3 h-1). Os valores indicaram que o aumento da taxa de diluição leva a um decréscimo da utilização de lactose e da produção de etanol e um aumento da produtividade volumétrica (QP). Valores semelhantes do fator de conversão de lactose em etanol (YEtOH/S) foram encontrados para todas as taxas de diluição testadas, em ambos sistemas de biorreator (fixo e fluidizado). A maior produtividade volumétrica foi obtida para a taxa de diluição de 0,3 h-1 em biorreator de leito fluidizado, alcançando 87% da conversão teórica, e a maior concentração de etanol (27,9 g L-1) foi obtida com a taxa de diluição de 0,1 h-1. As imagens de microscopia eletrônica de varredura (MEV) na superfície das esferas mostraram que a imobilização em alginato de cálcio foi eficaz. O estudo da transferência de massa da lactose e do etanol em esferas de cálcio foi realizado através da medição do coeficiente de difusão com base na abordagem matemática da Segunda Lei de Fick. Diferentes condições experimentais foram testadas. Os resultados obtidos mostraram que o coeficiente de difusão independe da concentração da solução de lactose (25, 50 e 75 g L-1) e de etanol (25 e 50 g L- 1), bem como da concentração de alginato (3, 4 e 6%), e que é afetado pela temperatura (25, 30 e 35 ºC), aumentando de 4,67×10-10 m2 s-1 a 6,96×10-10 m2 s-1 para a lactose, e de 1,46×10-10 m2 s-1 a 2,68×10-10 m2 s-1 para o etanol. / Cheese whey, an industrial by-product with highly pollutant characteristics, is a substrate for cell growth, rich in nutrients and with great potential for use in bioprocesses. The utilization of alternative and low cost substrates for the production of ethanol, such as industrial waste, has been recently studied with promising results. In this context, the aim of this work was to optimize the bioconversion of cheese whey into ethanol in bioreactors using immobilized Kluyveromyces marxianus as biocatalyst and evaluate the mass transfer limitations in Ca-alginate beads by measuring the diffusion coefficient. Similar ethanol yields (0.44±0.01 g EtOH g sugar-1) were found when testing the ethanol production by three strains of K. marxianus (CBS 6556, CCT 4086 and CCT 2653) in batch fluidized bed bioreactor, a decrease in conversion efficiency (83.3 to 66.1%) and ethanol productivity (0.96 to 0.78 g L- 1.h-1) was observed with the increase of fermentation temperature (30-40ºC) by immobilized K. marxianus CBS 6556. Continuous fluidized and packed bed bioreactors with different dilution rates (0.1 to 0.3 h-1) were performed. Values indicated that the increase of dilution rate led to a decrease in lactose utilization and ethanol production and an increase in ethanol productivity (QP). Similar ethanol yields (YEtOH/S) were obtained for all dilution rates tested, in both bioreactor systems. The highest ethanol productivity (3.5 g L-1h-1) was obtained at dilution rate of 0.3 h-1 in the fluidized bed bioreactor, with 87% of the theoretical conversion. The highest ethanol concentration (27.9 g L-1) was obtained at dilution rate of 0.1 h-1. The SEM micrographies of beads demonstrated that the cell immobilization in the Ca-alginate was effective. Lactose and ethanol mass transfer studies in Ca-alginate beads was performed by measuring the diffusion coefficient based on the mathematical approach of the Fick’s second Law. Different experimental conditions were tested. Results showed that diffusion coefficients were independent from the concentration of lactose (25, 50 and 75 g L-1) and ethanol (25 and 50 g L-1), as well as from the concentration of Ca-alginate (3, 4 and 6%), but were affected by temperature, increasing from 4.67×10-10 m2 s-1 to 6.96×10-10 m2 s-1 for lactose, and from 1.46×10-10 m2 s-1 to 2.68×10-10 m2 s-1 for ethanol.

Orientador: Florencia Cecilia Menegalli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-13T18:52:37Z (GMT). No. of bitstreams: 1 Monnerat_SandraMourao_D.pdf: 2359962 bytes, checksum: 3df7969a948ecae9b1a169de42e7087a (MD5) Previous issue date: 2009 / Resumo: No presente trabalho investigou-se a desidratação osmótica de maçãs (variedade Fuji), seguida ou não de secagem convectiva com ar quente. Foram determinados perfis de concentração de água e soluto(s) em amostras de maçãs cortadas ao meio e desidratadas osmoticamente em soluções aquosas binárias (30% e 50% de sacarose, p/p) e solução ternária (50% de sacarose e 10% de cloreto de sódio, m/m), sob agitação vigorosa e temperatura constante (27°C). As amostras imersas na solução osmótica durante 2, 4 e 8 h foram fatiadas a partir da superfície plana exposta. A densidade e os teores de água, açúcares totais e redutores e cloreto de sódio foram determinados em cada fatia. O modelo matemático que descreve o transporte de cada espécie estudada (água, sacarose e cloreto de sódio) se baseia na equação de continuidade e na Lei de Fick e considera o encolhimento do tecido. O modelo foi ajustado aos dados experimentais, através do método implícito de diferenças finitas de Crank-Nicolson para determinar os coeficientes efetivos de difusão como uma função da concentração, utilizando coordenadas materiais e integrando simultaneamente as equações diferenciais de cada componente (água e sacarose ou água, sacarose e cloreto de sódio). Imagens de microscopia ótica de tecidos tratados osmoticamente, previamente pigmentados com o corante vital vermelho neutro, foram obtidas variando-se a concentração das soluções e o tempo de exposição. Os registros fotográficos retratam alterações da estrutura celular, que variam de acordo com a intensidade do processo de desidratação. A secagem convectiva com ar quente foi realizada em amostras de maçãs cortadas ao meio, frescas e previamente tratadas em solução aquosa de sacarose a 50% p/p durante 4 horas (27°C). Os perfis de umidade foram determinados a partir da superfície, após a exposição da face plana das metades das maçãs ao fluxo de ar quente (60°C ) durante 3, 6, 10 e 24 horas de secagem. O modelo matemático que descreve o transporte da água se baseia nas equações de continuidade e na Lei de Fick e considera o encolhimento do tecido e a concentração inicial não homogênea para o tecido previamente tratado. De maneira similar à desidratação osmótica, a difusividade de água na secagem também foi determinada em função da concentração, utilizando-se o método implícito de diferenças finitas de Crank-Nicolson e coordenadas materiais. Obtevese um bom ajuste dos modelos matemáticos aos dados experimentais de desidratação osmótica e de secagem. A ordem de magnitude dos coeficientes obtidos para a desidratação osmótica foi uma ou duas vezes menor que de coeficientes de difusão binários de soluções puras de sacarose e de cloreto de sódio. No caso da secagem, o comportamento da difusividade mostrou dependência significativa com a concentração de água. O tecido fresco apresentou coeficientes superiores aos do tecido pré-tratado osmoticamente além de funcionalidades distintas para diferentes tempos de secagem (inferior e superior a 6 horas). O tecido tratado apresentou um comportamento mais estável da difusividade da água no material e foi descrito por uma única função. Este fato está relacionado com as mudanças estruturais ocorridas durante a secagem, mais severas para o tecido fresco em relação ao tecido tratado / Abstract: In this study it was investigated the osmotic dehydration of apples (Fuji variety) followed or not by convective drying with hot air. Concentration profiles were determined for water and solute(s) in samples of apples cut in half and osmotically dehydrated in binary aqueous solutions (30% and 50% sucrose, w/w) and ternary solution (50% sucrose and 10% sodium chloride, w/w) under vigorous stirring and constant temperature (27°C). The samples immersed in the osmotic solution for 2, 4 and 8 h were sliced from the exposed flat surface. The density and water, total and reducing sugars and sodium chloride contents were determined in each slice. The mathematical model that describes the transport of each species studied (water, sucrose and sodium chloride) is based on the continuity equation and on the of Fick's diffusion law and considers the tissue shrinkage. The model was fitted to experimental data through the finite difference implicit method of Crank-Nicolson, to determine the effective diffusion coefficients as a function of concentration, using material coordinates and integrating simultaneously the differential equations of each component (water and sucrose or water, sucrose and sodium chloride). Light microscopy images of osmotically processed tissues previously pigmented with the vital dye neutral red, were obtained, varying the concentration of solutions and time of exposure. The photographic records show changes in cellular structure, which vary with the intensity of the dehydration process. The convective air drying was carried out on samples of apples cut in half, fresh and treated in aqueous solution of sucrose to 50% w/w for 4 hours (27°C). The moisture profiles were determined from the surface, after exposure of the flat face of half of the apples to the flow of hot air (60 ° C) during 3, 6, 10 and 24 hours of drying. The mathematical model that describes the water transport is based on the continuity equation, the Fick's diffusion law, the tissue shrinkage and the nonhomogeneous initial concentration of the previously treated tissue. Similarly to the osmotic dehydration, the water diffusivity in drying was also determined in terms of concentration, using the finite difference implicit method of Crank-Nicolson and coordinated materials. It was possible to obtained a good fit of mathematical models to experimental data of osmotic dehydration and drying. The order of magnitude of the coefficients obtained for the osmotic dehydration was one or two times lower than diffusion coefficients of pure binary solutions of sucrose and sodium chloride. For drying, the behavior of diffusivity showed significant dependence with the concentration of water. The fresh tissue showed coefficients greater than the osmotically pre-treated tissue than it needs distinct functions for different times of drying (and less than 6 hours). The treated tissue showed a more stable behavior of the water diffusivity in the material and was described by a single function. This fact is related to the structural changes during drying, more severe for the fresh tissue than for the treated tissue / Doutorado / Doutor em Engenharia de Alimentos

Orientador: João Frederico da Costa Azevedo Meyer / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Matemática Estatística e Computação Científica / Made available in DSpace on 2018-08-24T22:34:38Z (GMT). No. of bitstreams: 1 Souza_JulianaMartaRodriguesde_D.pdf: 3368514 bytes, checksum: 4eec6362766752b87c0db7caebbeec84 (MD5) Previous issue date: 2014 / Resumo: O objetivo cumprido por esta tese é a criação e validação de uma técnica de recuperação de coeficientes de difusão para problemas ecológicos. O trabalho consta de oito capítulos e três deles são dedicados às ferramentas necessárias para a geração de dados sabidamente difusivos ou para o ajuste dos dados. Para a geração de dados trabalha-se com a obtenção da solução numérica de um problema difusivo tipicamente ecológico, combinando Elementos Finitos, Método de Galerkin e Crank-Nicolson. A seguir embasado-se no conceito de função densidade de probabilidade e em função de distribuição acumulada, lança-se mão do Método da Transformada Inversa. O Capítulo dedicado aos ajustes figura do trabalho para apresentar, ao leitor que ainda não havia tido contato, uma aplicação de um Algoritmo Genético. Tal algoritmo é usado para obter a solução de Quadrados Mínimos não-lineares em três parâmetros. A Regressão Linear tradicional, contando com apenas um parâmetro a ser ajustado também é utilizada. O principal conteúdo, o desenvolvimento do modelo e os resultados, excelentes, compõem mais dois Capítulos, o quinto e o sétimo, que, somados à Introdução, discussão sobre a bibliografia e Conclusão, fecham o trabalho. Discorre-se amplamente sobre o tipo de dado relativo a problemas ecológicos, e dificuldades inerentes, e sobre como o conhecimento sobre esse tipo de dados é fundamental no {\itshape design} do modelo. A cada passo dado, ferramenta desenvolvida ou introduzida, sua qualidade é atestada a fim de que, ao fim, a estrutura tenha sido construída sobre uma base sólida. O método recupera com sucesso coeficientes de difusão dentro de todo o espectro analisado, entre 0.0001 e 1 unidades de espaço ao quadrado por tempo; sendo possível tratar os dados de modo que a possibilidade de erro seja direcionada para uma hiper-estimativa, o que pode ser uma atitude previdente a depender do problema / Abstract: The goal attained by this thesis is the creation and validation of a diffusion coefficient, relative to ecological problems, recovery technique. Eight Chapters constitutes this work and three of them are dedicated to the tools needed for the diffusive related data generation or to the data fit. For the data generation, the numerical solution of a tipically ecological diffusive problem is obtained by combining Finite Elements, Galerkin's Method and Crank-Nicolson. Then, relying on the concepts of probability density function and cumulative distribution function, the Inverse Transform Method is applied. There is a Chapter dedicated to the fitting methods used here to introduce, to a reader who have not had the pleasure of meeting before, an application of a Genetic Algorithm. Such algorithm is used to obtain a non-linear Least Squares three parameter solution. The traditional Linear Regression is also used for fitting another version of the model. The main content, the development of the model and the excellent results compose two more Chapters, the fifth and the seventh that, when gathered to the Introduction, discussion about the bibliography and the Conclusion, closes the work. The kind of data related to ecological problems and the difficulties inherent to it are a main concern and deeply discussed. It is also focus of intense attention how the knowledge on this kind of data is fundamental for the method design. At each step, tool developed or introduced, its quality is attested with the purpose that, by the end of the work, the structure has been built on a solid basis. The method recovers succesfully diffusion coeficients with all the range analyzed, 0.0001 and 1 units of squared space over time; and it is also possible to determine the treatment for the data in such a way that error are directed to a hiper-estimative; that might be provident attitude depending on the problem / Doutorado / Matematica Aplicada / Doutora em Matemática Aplicada