The effects of vapor-grown carbon nanofiber (VGCNF) weight fraction, applied stress, and temperature on the viscoelastic responses (creep strain, creep rate, and creep compliance) of VGCNF/vinyl ester (VE) nanocomposites were studied using a central composite design (CCD). The nanocomposite test articles were fabricated by high shear mixing, casting, curing, and post-curing in an open face mold under a nitrogen environment. Short-term creep/creep recovery experiments were conducted at prescribed combinations of temperatures (23.8 – 69.2 C), applied stresses (30.2 – 49.8 MPa), and VGCNF weight fractions (0.00 – 1.00 parts of VGCNF per hundred parts of resin, phr) determined from the CCD. The response surface models (RSMs) for predicting these viscoelastic responses were developed using the least squares method and an analysis of variance procedure. The response surface estimates indicate that increasing the VGCNF weight fraction decreases the creep resistance of the VGCNF/VE nanocomposites at high temperatures (46.5 – 69.2 C).

No description available.

In many industrial experiments, completely randomized designs (CRDs) are impractical due to restrictions on randomization, or the existence of one or more hard-to-change factors. Under these situations, split-plot experiments are more realistic. The two separate randomizations in split-plot experiments lead to different error structure from in CRDs, and hence this affects not only response modeling but also the choice of design. In this dissertation, two graphical tools, three-dimensional variance dispersion graphs (3-D VDGs) and fractions of design space (FDS) plots are adapted for split-plot designs (SPDs). They are used for examining and comparing different variations of central composite designs (CCDs) with standard, V- and G-optimal factorial levels. The graphical tools are shown to be informative for evaluating and developing strategies for improving the prediction performance of SPDs. The overall cost of a SPD involves two types of experiment units, and often each individual whole plot is more expensive than individual subplot and measurement. Therefore, considering only the total number of observations is likely not the best way to reflect the cost of split-plot experiments. In this dissertation, cost formulation involving the weighted sum of the number of whole plots and the total number of observations is discussed and the three cost adjusted optimality criteria are proposed. The effects of considering different cost scenarios on the choice of design are shown in two examples. Often in practice it is difficult for the experimenter to select only one aspect to find the optimal design. A realistic strategy is to select a design with good balance for multiple estimation and prediction criteria. Variations of the CCDs with the best cost-adjusted performance for estimation and prediction are studied for the combination of D-, G- and V-optimality criteria and each individual criterion. / Ph. D.

Existe um número muito limitado de estudos referentes à produção de componentes antimicrobianos ou bacteriocinas produzidas por espécies de bifidobactérias. Nesse âmbito, o objetivo deste trabalho foi avaliar a produção de bifidobacteriocina em leite desnatado (LD). Para tanto, o estudo foi dividido em três etapas. A primeira etapa constituiu na preparação dos meios de cultura Man, Rogosa e Sharpe (MRS), Bifidus Selective Medium (BSM) e LD suplementado com 1% (p/v) de Tween 80 (T80), Inulina (I) ou Extrato de levedura (YE). Nesta etapa, os processos fermentativos foram conduzidos em shaker, nas condições: 50 rpm/37ºC/48h. Foram realizadas análises de pH, concentração de açúcares e ácidos, crescimento celular e determinação da atividade da bifidobacteriocina pelo método de difusão em ágar contra L. monocytogenes. Na segunda etapa, e baseado nos resultados obtidos, foi desenhado um delineamento composto central (CCD) construído a partir dos seguintes parâmetros: temperatura (34, 37, 40 °C) e concentração de YE (0,5; 1,0; 1,5 g/L). Na terceira etapa do trabalho, foram realizados os cultivos em biorreator de 2 L, contendo 10% de leite desnatado, nas seguintes condições: 200 rpm, 36°C, 2,0 g/L de YE, 48h de incubação em anaerobiose. Obteve-se em LD suplementado com YE (1%), combinado ao método de difusão em placa modificado (prévia refrigeração das placas por 12h), contra L. monocytogenes (2130 AU/mL), com uma fase exponencial de 24h, µm de 0,604/h. A otimização feita através do CCD permitiu atingir níveis de atividade de 3.000 AU/mL a 3.100 AU/mL (ensaios 7, 11 e 14, blocos 3 e 1) contra L. monocytogenes, em condições ótimas de crescimento de YE: 2,0 g/L1 e T°C: 36°C. A análise de regressão mostrou ser estatisticamente significativa a relação entre as variáveis: \"concentração de \"YE e temperatura\". Os resultados indicaram que o leite desnatado é um meio adequado para produção de bifidobacteriocina. / There are few publications that have been reported about bacteriocin production by Bifidobacterium species. Therefore, the aim of this work was measure bacteriocin production in skim milk by B. lactis. Consequently, this work was divided in three stages. First, MRS, BSM and LD medium were tested with additives (Tween 80 (T80), Inuline (I) or Yeast extract (YE)) for bacteriocin production and cellular growth. Fermentation processes were conducted in shaker under specific conditions: 50 rpm/37ºC/48h. pH; sugars; acids; biomass, and bacteriocin activity against L. monocytogenes, L. plantarum, E. coli, L. sakei e S. aureus strains were analyzed . In the second stage, based on the obtained results, a central composite design (CCD) was created using the parameters: temperature (34, 37, 40 ºC), and concentration of YE (0.5, 1.0, 1.5 g/L). After, the activity was measured by two methods of plates pre-diffusion (cooling and addition of Tween 20). Third step consisted of 2 L bioreactor cultivations containing 10% skim milk diluted in 1.5 L of water (6.5 pH), under 200 rpm, 36 ºC, 2.0 g/L of YE, 48h, under anaerobic condition. Finally, the cultures supplemented with LD and YE (1%) with a modified plate diffusion method (cooling plates for 12 h) showed bacteriocin activity against L. monocytogenes (2130 AU/mL) with an exponential phase of 24 h, µm of 0.604/h. The optimization performed using CCD resulted in a higher level of activity 3000 AU/mL to 3100 AU/mL mL (Run 7, 11 and 14, blocks 3 and 1) against L. monocytogenes, also with ideal growth conditions of YE: 2,0 g/L1 and T °C: 36 °C. The pH value varied between 6.4 and 4.0. Concentration of produced acid lactic varied from 3.03 to 4.72 g/L and biomass concentration from 3.4 to 11.1 Lg UFC/mL. Regression analysis was significant to the variables: YE concentration and temperature. Results indicated that skim milk is a proper medium for \"Bifidobacteriocin\" production.

Made available in DSpace on 2017-07-21T18:53:04Z (GMT). No. of bitstreams: 1 CRISTIANE BOURSCHEID.pdf: 1448163 bytes, checksum: 21f79c9c1335f39830bfef99ee3f5f19 (MD5) Previous issue date: 2015-03-11 / The chicken slaughterhouse generate co-products during slaughter, for example, feathers, bones, blood and guts, usually intended for animal feed with low added value. In bone part of the meat remains bound even after deboning and is a good source of substrate for the enzymatic hydrolysis. The protein hydrolysates may be applied as a nutritional supplement in foods. Given this context, the objective was to optimize the enzymatic hydrolysis process for obtaining protein hydrolyzate coproduct of chicken bones (Gallus gallus domesticus) and the addition of the hydrolyzate as a protein supplement in burger. The co-product selected to carry out the work was thigh and drumstick bone from the chicken bones in a slaughterhouse. The study was conducted in two stages. In the first one a central composite design (CCRD), a total of 17 tests was adopted to evaluate the influence of temperature, enzyme: substrate ratio and time on the degree of hydrolysis. Following the statistical optimization was performed to obtain the best conditions of enzymatic hydrolysis of co-product of chicken bones. The co-product of chicken bones and the optimized protein hydrolyzate were characterized in terms of chemical composition, total amino acids and pattern. In the second step, the hydrolyzate was added as a protein supplement in poultry burger, where two formulations were prepared, Hamburger control (no addition of protein hydrolyzate) and hamburger with hydrolyzed (with addition of 8% protein hydrolyzate). The burgers were characterized in terms of physical-chemical, microbiological and sensory analysis. The optimum conditions for the enzymatic hydrolysis were temperature (T) of 50 ° C, enzyme: substrate ratio (E:S) from 4.96% to time (t) of 110.16 minutes under these conditions the degree of hydrolysis was 24, 0.22 ± 21%. The protein hydrolyzate has the potential to supplementation in food, it is good source of essential amino acids, meeting the recommendations established by FAO / WHO, except for leucine, phenylalanine, and valine, and had a higher concentration of protein fractions from 14.437 kDa and 3,496 kDa. The results obtained for microbiological analysis and physical-chemical analysis of the burger control and burger with hydrolyzed, are in accordance with the respective standards set by law. The burger with hydrolyzate showed 1.02% more protein than the burger control, giving a protein supplementation to the product developed. In the sensorial analysis for flavor attribute evaluators preferred the burger with protein hydrolyzate. The burger with protein hydrolyzate and the burger control achieved 84.2% and 81.8% of general acceptance, respectively. The intention to buy for the burger with added protein hydrolyzate was 76.4% and for the burger control was 67%. In this light, the protein hydrolyzate obtained from chicken bones of the co-product is an alternative to supplementation in foods, as well as add value to the co-product of chicken dessosa and increase the competitiveness of slaughterhouse. / Os frigoríficos de frango geram coprodutos durante o abate, por exemplo, penas, ossos, sangue e vísceras, geralmente, destinados para ração animal com baixo valor agregado. Uma parte de carne permanece aderida aos ossos, mesmo após a desossa, sendo uma boa fonte de substrato para a hidrólise enzimática. Os hidrolisados proteicos podem ser aplicados como suplemento nutricional em alimentos. Diante desse contexto, o objetivo do trabalho foi otimizar o processo de hidrólise enzimática para obtenção de hidrolisado proteico de coproduto da desossa de frango (Gallus gallus domesticus) e a adição do hidrolisado como suplemento proteico em hambúrguer. O coproduto selecionado para realização do trabalho foi osso de coxa e sobrecoxa proveniente da desossa de frango em frigorífico. O trabalho foi realizado em duas etapas. Na primeira um delineamento composto central rotacional (DCCR), totalizando 17 ensaios foi adotado para avaliar a influência da temperatura, relação enzima:substrato e tempo sobre o grau de hidrólise. Na sequência, foi realizada a otimização estatística para obter as melhores condições da hidrólise enzimática. O coproduto da desossa de frango e o hidrolisado proteico otimizado foram caracterizados em termos de composição centesimal, aminoácidos totais e perfil eletroforético. Na segunda etapa, o hidrolisado foi adicionado como suplemento proteico em hambúrguer de frango. Foram elaboradas duas formulações, hambúrguer controle (sem adição de hidrolisado proteico) e hambúrguer com hidrolisado (com adição de 8% de hidrolisado proteico). Os hambúrgueres foram caracterizados em termos de análises físico-químicas, análises microbiológicas e análise sensorial. As condições ótimas para a hidrólise enzimática foram temperatura (T) de 50ºC, relação enzima:substrato (E:S) de 4,96% e tempo (t) de 110,16 minutos, nessas condições o grau de hidrólise foi de 24,21% ±0,22. O hidrolisado proteico apresentou potencial para suplementação em alimentos, pois é boa fonte de aminoácidos essenciais, atendendo as recomendações estabelecidas pela FAO/WHO, exceto para leucina, fenilalanina e valina, bem como apresentou maior concentração de frações proteicas entre 14,437 kDa e 3,496 kDa. Os resultados obtidos para a análise microbiológica e análises físico-químicas do hambúrguer controle e do hambúrguer com hidrolisado, estão de acordo com os respectivos padrões estabelecidos pela legislação vigente. O hambúrguer com hidrolisado apresentou 6% mais proteína do que o hambúrguer controle, conferindo uma suplementação proteica ao produto desenvolvido. Em relação à análise sensorial para o atributo sabor, os avaliadores preferiram o hambúrguer com hidrolisado proteico. O hambúrguer com hidrolisado proteico e o hambúrguer controle obtiveram 84,2% e 81,8% de aceitação geral, respectivamente. A intenção de compra para o hambúrguer com adição de hidrolisado proteico foi de 76,4% e para o hambúrguer controle foi de 67%. Diante do exposto, o hidrolisado proteico obtido a partir de coproduto da desossa de frango é uma alternativa para a suplementação em alimentos, além de agregar valor ao coproduto da dessosa de frango e aumentar a competitividade dos frigoríficos.

Made available in DSpace on 2017-07-10T19:25:09Z (GMT). No. of bitstreams: 1 Michael.pdf: 1358064 bytes, checksum: 7b7dc640218999c74c7f3b747a92d228 (MD5) Previous issue date: 2012-02-20 / In the twenty-first century, the broiler production has increased in the world and continues increasing due to the high consumption of this meat. The broiler litter is the largest amount of waste generated in poultry production. It is also characterized by its high concentration of organic matter. The broiler production integrated system defines a radius around it to settle down poultry farms in order to reduce costs. It has also increased the concentration of broiler litter in the producing regions and demanded waste treatment. So, the anaerobic digestion has come as an alternative treatment with high organic load removal. Thus, this trial aimed at evaluating the treatment capacity of broiler litter by anaerobic digestion into tubular biodigester with a semi-continuous flow. The applied treatments varied both the amount of added total volatile solids, from 2.93 to 3.72%, as well as the hydraulic retention time, from 11.60 to 28.40 days. The digesters were maintained at 27 ºC and considered stabilized when the removal efficiency of total solids, total volatile solids and chemical oxygen demand were according to the statistical quality control. Once stabilized, the 11 digesters of 0.6 m per 0.15 m (length per diameter) were evaluated for removal of solids and chemical oxygen demand with statistical quality control and design composite central rotational in a factorial design (22), at two levels (-1, 1), plus the axial points (-α, α) and the central point. The analysis of statistical quality control showed that the treatment with 3.32% added total volatile solids and 20 days of hydraulic retention time removed the highest amount of total solids (64.37%) and total volatile solids (72.38%), while the removal values of chemical oxygen demand were similar in all treatments, around 80%. Significant statistical models were registered with the central composite rotational design to remove total solids and for chemical oxygen demand. / No século XXI, a produção de frangos de corte ganhou espaço no mercado e continua crescendo, devido ao alto consumo da carne. A cama de frango é o resíduo gerado em maior quantidade na produção de frangos e caracteriza-se pela elevada concentração de matéria orgânica. O sistema de produção de frango de corte das empresas integradoras delimita um raio ao seu redor para implantação de aviários, visando à redução de custos, além de ocasionar a concentração de cama de frango nas regiões produtoras e gerar a necessidade de tratar o resíduo. A digestão anaeróbia é uma alternativa de tratamento, com alta remoção de carga orgânica. Logo, o objetivo deste trabalho foi avaliar a capacidade de tratamento da digestão anaeróbia da cama de frango em biodigestor tubular de fluxo semicontínuo. Os tratamentos aplicados variaram tanto a quantidade de sólidos totais voláteis adicionados, de 2,93 a 3,72% como o tempo de detenção hidráulica, de 11,60 a 28,40 dias. Os biodigestores foram mantidos a 27 ºC e considerados estabilizados quando as eficiências de remoção de sólidos totais, sólidos totais voláteis e demanda química de oxigênio encontraram-se dentro do controle estatístico de qualidade. Depois de estabilizados, os onze biodigestores de 0,60 m por 0,15 m (comprimento x diâmetro) foram avaliados quanto à remoção de sólidos e à demanda química de oxigênio com o controle estatístico de qualidade. O delineamento composto central rotacional foi em esquema fatorial (22), em dois níveis (1, +1), mais os pontos axiais (-α, +α) e o ponto central. A análise do controle estatístico de qualidade mostrou que o tratamento com 3,32% de sólidos totais voláteis adicionados e 20 dias de tempo de detenção hidráulica foi o que mais se destacou na remoção de sólidos totais (64,37%) e sólidos totais voláteis (72,38%) e os valores de remoção de demanda química de oxigênio foram próximos em todos os tratamentos, em torno de 80%. Com o delineamento composto central rotacional, foram verificados modelos estatísticos significativos para a remoção de sólidos totais e demanda química de oxigênio.

Made available in DSpace on 2017-05-12T14:48:32Z (GMT). No. of bitstreams: 1 Michael.pdf: 1358064 bytes, checksum: 7b7dc640218999c74c7f3b747a92d228 (MD5) Previous issue date: 2012-02-20 / In the twenty-first century, the broiler production has increased in the world and continues increasing due to the high consumption of this meat. The broiler litter is the largest amount of waste generated in poultry production. It is also characterized by its high concentration of organic matter. The broiler production integrated system defines a radius around it to settle down poultry farms in order to reduce costs. It has also increased the concentration of broiler litter in the producing regions and demanded waste treatment. So, the anaerobic digestion has come as an alternative treatment with high organic load removal. Thus, this trial aimed at evaluating the treatment capacity of broiler litter by anaerobic digestion into tubular biodigester with a semi-continuous flow. The applied treatments varied both the amount of added total volatile solids, from 2.93 to 3.72%, as well as the hydraulic retention time, from 11.60 to 28.40 days. The digesters were maintained at 27 ºC and considered stabilized when the removal efficiency of total solids, total volatile solids and chemical oxygen demand were according to the statistical quality control. Once stabilized, the 11 digesters of 0.6 m per 0.15 m (length per diameter) were evaluated for removal of solids and chemical oxygen demand with statistical quality control and design composite central rotational in a factorial design (22), at two levels (-1, 1), plus the axial points (-α, α) and the central point. The analysis of statistical quality control showed that the treatment with 3.32% added total volatile solids and 20 days of hydraulic retention time removed the highest amount of total solids (64.37%) and total volatile solids (72.38%), while the removal values of chemical oxygen demand were similar in all treatments, around 80%. Significant statistical models were registered with the central composite rotational design to remove total solids and for chemical oxygen demand. / No século XXI, a produção de frangos de corte ganhou espaço no mercado e continua crescendo, devido ao alto consumo da carne. A cama de frango é o resíduo gerado em maior quantidade na produção de frangos e caracteriza-se pela elevada concentração de matéria orgânica. O sistema de produção de frango de corte das empresas integradoras delimita um raio ao seu redor para implantação de aviários, visando à redução de custos, além de ocasionar a concentração de cama de frango nas regiões produtoras e gerar a necessidade de tratar o resíduo. A digestão anaeróbia é uma alternativa de tratamento, com alta remoção de carga orgânica. Logo, o objetivo deste trabalho foi avaliar a capacidade de tratamento da digestão anaeróbia da cama de frango em biodigestor tubular de fluxo semicontínuo. Os tratamentos aplicados variaram tanto a quantidade de sólidos totais voláteis adicionados, de 2,93 a 3,72% como o tempo de detenção hidráulica, de 11,60 a 28,40 dias. Os biodigestores foram mantidos a 27 ºC e considerados estabilizados quando as eficiências de remoção de sólidos totais, sólidos totais voláteis e demanda química de oxigênio encontraram-se dentro do controle estatístico de qualidade. Depois de estabilizados, os onze biodigestores de 0,60 m por 0,15 m (comprimento x diâmetro) foram avaliados quanto à remoção de sólidos e à demanda química de oxigênio com o controle estatístico de qualidade. O delineamento composto central rotacional foi em esquema fatorial (22), em dois níveis (1, +1), mais os pontos axiais (-α, +α) e o ponto central. A análise do controle estatístico de qualidade mostrou que o tratamento com 3,32% de sólidos totais voláteis adicionados e 20 dias de tempo de detenção hidráulica foi o que mais se destacou na remoção de sólidos totais (64,37%) e sólidos totais voláteis (72,38%) e os valores de remoção de demanda química de oxigênio foram próximos em todos os tratamentos, em torno de 80%. Com o delineamento composto central rotacional, foram verificados modelos estatísticos significativos para a remoção de sólidos totais e demanda química de oxigênio.

Existe um número muito limitado de estudos referentes à produção de componentes antimicrobianos ou bacteriocinas produzidas por espécies de bifidobactérias. Nesse âmbito, o objetivo deste trabalho foi avaliar a produção de bifidobacteriocina em leite desnatado (LD). Para tanto, o estudo foi dividido em três etapas. A primeira etapa constituiu na preparação dos meios de cultura Man, Rogosa e Sharpe (MRS), Bifidus Selective Medium (BSM) e LD suplementado com 1% (p/v) de Tween 80 (T80), Inulina (I) ou Extrato de levedura (YE). Nesta etapa, os processos fermentativos foram conduzidos em shaker, nas condições: 50 rpm/37ºC/48h. Foram realizadas análises de pH, concentração de açúcares e ácidos, crescimento celular e determinação da atividade da bifidobacteriocina pelo método de difusão em ágar contra L. monocytogenes. Na segunda etapa, e baseado nos resultados obtidos, foi desenhado um delineamento composto central (CCD) construído a partir dos seguintes parâmetros: temperatura (34, 37, 40 °C) e concentração de YE (0,5; 1,0; 1,5 g/L). Na terceira etapa do trabalho, foram realizados os cultivos em biorreator de 2 L, contendo 10% de leite desnatado, nas seguintes condições: 200 rpm, 36°C, 2,0 g/L de YE, 48h de incubação em anaerobiose. Obteve-se em LD suplementado com YE (1%), combinado ao método de difusão em placa modificado (prévia refrigeração das placas por 12h), contra L. monocytogenes (2130 AU/mL), com uma fase exponencial de 24h, µm de 0,604/h. A otimização feita através do CCD permitiu atingir níveis de atividade de 3.000 AU/mL a 3.100 AU/mL (ensaios 7, 11 e 14, blocos 3 e 1) contra L. monocytogenes, em condições ótimas de crescimento de YE: 2,0 g/L1 e T°C: 36°C. A análise de regressão mostrou ser estatisticamente significativa a relação entre as variáveis: \"concentração de \"YE e temperatura\". Os resultados indicaram que o leite desnatado é um meio adequado para produção de bifidobacteriocina. / There are few publications that have been reported about bacteriocin production by Bifidobacterium species. Therefore, the aim of this work was measure bacteriocin production in skim milk by B. lactis. Consequently, this work was divided in three stages. First, MRS, BSM and LD medium were tested with additives (Tween 80 (T80), Inuline (I) or Yeast extract (YE)) for bacteriocin production and cellular growth. Fermentation processes were conducted in shaker under specific conditions: 50 rpm/37ºC/48h. pH; sugars; acids; biomass, and bacteriocin activity against L. monocytogenes, L. plantarum, E. coli, L. sakei e S. aureus strains were analyzed . In the second stage, based on the obtained results, a central composite design (CCD) was created using the parameters: temperature (34, 37, 40 ºC), and concentration of YE (0.5, 1.0, 1.5 g/L). After, the activity was measured by two methods of plates pre-diffusion (cooling and addition of Tween 20). Third step consisted of 2 L bioreactor cultivations containing 10% skim milk diluted in 1.5 L of water (6.5 pH), under 200 rpm, 36 ºC, 2.0 g/L of YE, 48h, under anaerobic condition. Finally, the cultures supplemented with LD and YE (1%) with a modified plate diffusion method (cooling plates for 12 h) showed bacteriocin activity against L. monocytogenes (2130 AU/mL) with an exponential phase of 24 h, µm of 0.604/h. The optimization performed using CCD resulted in a higher level of activity 3000 AU/mL to 3100 AU/mL mL (Run 7, 11 and 14, blocks 3 and 1) against L. monocytogenes, also with ideal growth conditions of YE: 2,0 g/L1 and T °C: 36 °C. The pH value varied between 6.4 and 4.0. Concentration of produced acid lactic varied from 3.03 to 4.72 g/L and biomass concentration from 3.4 to 11.1 Lg UFC/mL. Regression analysis was significant to the variables: YE concentration and temperature. Results indicated that skim milk is a proper medium for \"Bifidobacteriocin\" production.

Pervaporation (PV), a non-porous membrane separation process, is gaining considerable attention for solvent separation in a variety of industries ranging from chemical to food and pharmaceutical to petrochemicals. The most successful application has been the dehydration of organic liquids, for which hydrophilic membranes are used. However, during pervaporation, excessive affinity of water towards hydrophilic membranes leads to undesirable swelling (water absorption) of the membrane matrix. To control swelling, often hydrophilic membranes are crosslinked to modify physicochemical (surface and bulk) properties. Since the transport of species in pervaporation is governed by sorption (affected by surface and bulk properties) and diffusion (affected by bulk properties), it is essential to study the effect of crosslinking on the surface and bulk physicochemical properties and their effects on separation performance. This thesis focuses on the effect of crosslinking on the physicochemical properties (e.g., crystallinity, hydrophilicity, surface roughness) of hydrophilic polymeric membranes and their dehydration performance alcohol-water mixtures. Poly(vinyl alcohol), PVA was used as the base polymer to prepare membranes with various morphologies such as homogeneous, blended (with Chitosan, CS) and composite (with poly(sulfone), PSf) structures. Before applying the crosslinked membranes for the PV dehydration of alcohols, the physicochemical characterization were carried out using Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), tensile testing, contact angle and swelling experiments. The crosslinked membranes showed an increase in surface hydrophobicity from the contact angle measurements as compared to the uncrosslinked membranes. AFM surface topography showed that the membrane surfaces have nodular structures and are rough at the nanometer scale and affected by the crosslinking conditions such as concentration and reaction time. Surface hydrophobicity and roughness was found to increase with increasing degree of crosslinking. DSC measurements showed an increase in melting temperature of the polymer membranes after crosslinking. For the PV dehydration of ethanol, a decrease in flux and an increase in selectivity were observed with increase in the degree of crosslinking. Effects of membrane thickness (of PVA layer) for crosslinked PVA-PSf composite membranes were studied on PV dehydration of ethanol. Total flux and selectivity were statistically analyzed as a function of the membrane thickness. In general, the outcome agrees with the solution-diffusion (S-D) theory: the total flux was found to be significantly affected by the PVA layer thickness, while the selectivity remains nearly unaffected. Using the S-D theory, the mass transfer resistance of the selective layers was calculated and found to increase with thickness. The relatively small change observed for selectivity has been related to the crosslinking of the PVA layer that increases the surface hydrophobicity of the membrane. Chitosan-Poly(vinyl alcohol), or CS-PVA, blended membranes were prepared by varying the blending ratio to control membrane crystallinity and its effect on the PV dehydration of ethylene glycol. The blended membranes were crosslinked interfacially with trimesoyl chloride (TMC)/hexane. The crystallinity of the membrane was found to decrease with increasing CS wt% in the blend. Although the crosslinked CS-PVA blend membranes showed improved mechanical strength, they became less flexible as detected in tensile testing. The resulting crosslinked CS-PVA blended membranes showed high flux and selectivity simultaneously, for 70-80wt% CS in the blend. The effect of feed flow-rate was studied to find the presence of concentration polarization for 90wt% EG in feed mixture as well. The crosslinked blend membrane with 75wt% CS showed a highest total flux of 0.46 kg/m2/h and highest selectivity of 663 when operating at 70oC with 90wt% EG in the feed mixture. Effects of crosslinking concentration and reaction time of trimesoyl chloride (TMC) were studied on poly(vinyl alcohol)-poly(sulfone) or PVA-PSf composite membranes. Results showed a consistent trend of changes in the physicochemical properties: the degree of crosslinking, crystallinity, surface roughness, hydrophilicity and swelling degree all decrease with increasing crosslinking agent (TMC) concentration and reaction time. The crosslinked membrane performance was assessed with PV dehydration of ethylene glycol-water mixtures at a range of concentrations (30 to 90wt% EG). The total flux of permeation was found to decrease, while the selectivity to increase, with increasing TMC concentration and reaction time. The decrease in flux was most prominent at low EG concentrations in the feed mixtures. A central composite rotatable design (CCRD) of response surface methodology was used to analyze PV dehydration performance of crosslinked poly(vinyl alcohol) (PVA) membranes. Regression models were developed for the flux and selectivity as a function of operating conditions such as, temperature, feed alcohol concentration, and flow-rate. Dehydration experiments were performed on two different alcohol-water systems: isopropanol-water (IPA-water) and ethanol-water (Et-water) mixtures around the azeotrope concentrations. Judged by the lack-of-fit criterion, the analysis of variance (ANOVA) showed the regression model to be adequate. The predicted flux and selectivity from the regression models were presented in 3-D surface plots over the whole ranges of operating variables. For both alcohol-water systems, quadratic effect of temperature and feed alcohol concentration showed significant (p < 0.0001) influence on the flux and selectivity. A strong interaction effect of temperature and concentration was observed on the selectivity for the Et-water system. For the dehydration of azeotropic IPA-water mixture (87.5wt% IPA), the optimized dehydration variables were found to be 50.5oC and 93.7 L/hr for temperature and flow-rate, respectively. On the other hand for azeotropic Et-water mixture (95.5wt% Et), the optimized temperature and flow-rate were found to be 57oC and 89.2 L/hr, respectively. Compared with experiments performed at optimized temperature and feed flow-rate, the predicted flux and selectivity of the azeotropic mixtures showed errors to be within 3-6 %.

Pervaporation (PV), a non-porous membrane separation process, is gaining considerable attention for solvent separation in a variety of industries ranging from chemical to food and pharmaceutical to petrochemicals. The most successful application has been the dehydration of organic liquids, for which hydrophilic membranes are used. However, during pervaporation, excessive affinity of water towards hydrophilic membranes leads to undesirable swelling (water absorption) of the membrane matrix. To control swelling, often hydrophilic membranes are crosslinked to modify physicochemical (surface and bulk) properties. Since the transport of species in pervaporation is governed by sorption (affected by surface and bulk properties) and diffusion (affected by bulk properties), it is essential to study the effect of crosslinking on the surface and bulk physicochemical properties and their effects on separation performance. This thesis focuses on the effect of crosslinking on the physicochemical properties (e.g., crystallinity, hydrophilicity, surface roughness) of hydrophilic polymeric membranes and their dehydration performance alcohol-water mixtures. Poly(vinyl alcohol), PVA was used as the base polymer to prepare membranes with various morphologies such as homogeneous, blended (with Chitosan, CS) and composite (with poly(sulfone), PSf) structures. Before applying the crosslinked membranes for the PV dehydration of alcohols, the physicochemical characterization were carried out using Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-Ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), tensile testing, contact angle and swelling experiments. The crosslinked membranes showed an increase in surface hydrophobicity from the contact angle measurements as compared to the uncrosslinked membranes. AFM surface topography showed that the membrane surfaces have nodular structures and are rough at the nanometer scale and affected by the crosslinking conditions such as concentration and reaction time. Surface hydrophobicity and roughness was found to increase with increasing degree of crosslinking. DSC measurements showed an increase in melting temperature of the polymer membranes after crosslinking. For the PV dehydration of ethanol, a decrease in flux and an increase in selectivity were observed with increase in the degree of crosslinking. Effects of membrane thickness (of PVA layer) for crosslinked PVA-PSf composite membranes were studied on PV dehydration of ethanol. Total flux and selectivity were statistically analyzed as a function of the membrane thickness. In general, the outcome agrees with the solution-diffusion (S-D) theory: the total flux was found to be significantly affected by the PVA layer thickness, while the selectivity remains nearly unaffected. Using the S-D theory, the mass transfer resistance of the selective layers was calculated and found to increase with thickness. The relatively small change observed for selectivity has been related to the crosslinking of the PVA layer that increases the surface hydrophobicity of the membrane. Chitosan-Poly(vinyl alcohol), or CS-PVA, blended membranes were prepared by varying the blending ratio to control membrane crystallinity and its effect on the PV dehydration of ethylene glycol. The blended membranes were crosslinked interfacially with trimesoyl chloride (TMC)/hexane. The crystallinity of the membrane was found to decrease with increasing CS wt% in the blend. Although the crosslinked CS-PVA blend membranes showed improved mechanical strength, they became less flexible as detected in tensile testing. The resulting crosslinked CS-PVA blended membranes showed high flux and selectivity simultaneously, for 70-80wt% CS in the blend. The effect of feed flow-rate was studied to find the presence of concentration polarization for 90wt% EG in feed mixture as well. The crosslinked blend membrane with 75wt% CS showed a highest total flux of 0.46 kg/m2/h and highest selectivity of 663 when operating at 70oC with 90wt% EG in the feed mixture. Effects of crosslinking concentration and reaction time of trimesoyl chloride (TMC) were studied on poly(vinyl alcohol)-poly(sulfone) or PVA-PSf composite membranes. Results showed a consistent trend of changes in the physicochemical properties: the degree of crosslinking, crystallinity, surface roughness, hydrophilicity and swelling degree all decrease with increasing crosslinking agent (TMC) concentration and reaction time. The crosslinked membrane performance was assessed with PV dehydration of ethylene glycol-water mixtures at a range of concentrations (30 to 90wt% EG). The total flux of permeation was found to decrease, while the selectivity to increase, with increasing TMC concentration and reaction time. The decrease in flux was most prominent at low EG concentrations in the feed mixtures. A central composite rotatable design (CCRD) of response surface methodology was used to analyze PV dehydration performance of crosslinked poly(vinyl alcohol) (PVA) membranes. Regression models were developed for the flux and selectivity as a function of operating conditions such as, temperature, feed alcohol concentration, and flow-rate. Dehydration experiments were performed on two different alcohol-water systems: isopropanol-water (IPA-water) and ethanol-water (Et-water) mixtures around the azeotrope concentrations. Judged by the lack-of-fit criterion, the analysis of variance (ANOVA) showed the regression model to be adequate. The predicted flux and selectivity from the regression models were presented in 3-D surface plots over the whole ranges of operating variables. For both alcohol-water systems, quadratic effect of temperature and feed alcohol concentration showed significant (p < 0.0001) influence on the flux and selectivity. A strong interaction effect of temperature and concentration was observed on the selectivity for the Et-water system. For the dehydration of azeotropic IPA-water mixture (87.5wt% IPA), the optimized dehydration variables were found to be 50.5oC and 93.7 L/hr for temperature and flow-rate, respectively. On the other hand for azeotropic Et-water mixture (95.5wt% Et), the optimized temperature and flow-rate were found to be 57oC and 89.2 L/hr, respectively. Compared with experiments performed at optimized temperature and feed flow-rate, the predicted flux and selectivity of the azeotropic mixtures showed errors to be within 3-6 %.