The objective of this PhD project is to develop novel membranes and desiccants that would help develop a second generation vacuum desiccant cooling (VDC) garment that is efficient, robust, durable and wearer-friendly. It was found that properly chosen support material could improve both mechanical strength and vapor flux for flat sheet polyvinylidene fluoride (PVDF), due to improved membrane structure and structure integrity that enhanced vapour mass transfer. Super solid desiccants were developed using a super absorbent polymer (SAP), which are sodium polyacrylate granules, as the host matrices to harbour LiCl. Furthermore, a novel desiccant based on loading LiCl in to hydrophobic hollow fibre membranes and therefore called membrane based desiccant fiber (MDF), was developed and demonstrated to be suitable for VDC. Heat and mass transfer for vapor absorption in MDF were analyzed. These membranes and desiccants, although developed for application in VDC, may also found applications in other fields such as water treatment, air conditioning, and natural gas dehumidification. Finally, based on the newly developed membranes and desiccants, three conceptual designs of second generation VDC garments are proposed.

L'objectif de ce travail était d'étudier les trois fonctions d'une colonne airlift sous dépression qui sont le pompage, les transferts gaz-liquide et l'extraction de matières particulaires par moussage-écumage. Le champ d'application ciblé concernait principalement le traitement des eaux aquacoles incluant l'extraction et la concentration de microalgues naturelles ou de culture. Chacune des fonctions a été étudiée séparément afin d'évaluer les capacités de l'airlift dans différentes conditions. L'étude de la fonction pompage a montré l'importance de la nature de l'eau, du type de diffuseur d'air, du débit gazeux injecté et du niveau de dépression appliqué. En eau douce, une forte coalescence des bulles est observée. Elle a pour conséquence une rétention gazeuse plus faible qu'en eau de mer. Le débit d'eau fourni par la colonne apparaît ainsi supérieur en eau douce (30 à 35 m3.h-1 contre seulement 10 à 20 m3.h-1 en eau de mer pour 5 m3.h-1 d'air injecté). A l'inverse, la hauteur de refoulement disponible est plus élevée en eau de mer (jusqu'à 0.8 m) qu'en eau douce (0.6 m maximum). Pour des circuits d'aquaculture où la perte de charge est faible, l'airlift est un système de pompage économique qui permet de réduire d'environ 40 % la consommation d'énergie par rapport à celle de pompes centrifuges. La colonne airlift présente également des capacités de transferts de matière comparables à celles de systèmes conventionnels. Les valeurs de KLa calculées pour la désorption du CO2 et comprises entre 0.002 et 0.01 s-1, sont environ quatre fois inférieures à celles obtenues pour le transfert d'oxygène par aération dans des conditions comparables. Les efficacités de transfert sont comprises entre 0.02 et 0.023 Kg.KW.h-1 pour le CO2 et entre 1.52 et 1.8 Kg.KW.h-1 pour l'O2. Les vitesses de transfert dépendent significativement du débit d'air, de la température, de la taille moyenne des bulles et de la présence d'aliments dans le bassin d'élevage. Elles sont peu affectées par la salinité, le niveau de dépression, la longueur du tube interne d'échange et le débit d'eau. Enfin, les capacités de séparation par moussage-écumage évoluent de façon positive quand le débit d'air et la taille des bulles sont réduits. L'efficacité globale d'extraction diminue avec l'augmentation de la concentration des produits extraits qui peut atteindre 130 fois la concentration initiale. La colonne à dépression apparaît ainsi comme un système multifonctionnel performant, même si l'efficacité maximale, pour chacune des fonctions, correspond à des conditions opératoires différentes. Ce procédé ouvre des perspectives de développement intéressantes dans des secteurs variés (de l'aquaculture au traitement des eaux industrielles). / The aim of this work was to study the three functions of a vacuum airlift, which are water pumping, mass transfer and foam fractionation. The investigations mainly focused on the treatment of fish culture water and on phytoplancton harvesting. Each function was studied separately, in order to assess the performance of the vacuum airlift with specific operating conditions. By studying the airlift pump, the effects of water and diffuser types, air injection conditions and depression level were shown. In fresh water, bubble coalescence was observed, which reduced gas holdup compared to sea water. Consequently, the water flow of the vacuum airlift appeared higher in fresh water than in sea water (30 to 35 m3.h-1 against 10 to 20 m3.h-1) for the same air flow rate (5 m3.h-1). Conversely, the available lift height was higher in sea water (up to 0.8 m) than in fresh water (0.6 m maximum). For low head aquaculture systems, the vacuum airlift may be an economical pumping system which allows a 40 % energy saving compared to centrifugal pumps. The vacuum airlift had a mass transfer efficiency similar to other gas transfer systems. The KLa values calculated for CO2 desorption ranged between 0.002 and 0.01 s-1. They were four times lower than those obtained for oxygen transfer in similar conditions. Mass transfer efficiencies ranged between 0.02 and 0.023 Kg.KW.h-1 for CO2 and between 1.52 and 1.8 Kg.KW.h-1 for O2. Mass transfer velocities significantly depended on air flow rate, water temperature, average bubble size and the presence of feed in the rearing tank. They are weakly depending on salinity, depression level, inner tube length or water flow. At last, foam fractionation increased when air flow and bubble size were reduced. The extraction efficiency decreased when the concentration of the extracted product increased (maximal concentration factor around130). The vacuum airlift appeared to be as a high-performance multifunctional system, even if the maximal efficiency for each of the functions corresponds to different operating conditions. This process could be used in a large scope of fields ranging from aquaculture to industrial water treatment.

Le marinage et le saumurage améliorent la durée de conservation, la tendreté et la jutosité de la viande et du poisson. En complément, un malaxage ou « barattage » est souvent appliqué aux pièces de viande préalablement à la cuisson. Le but principal de cette étude était d’évaluer l’impact des conditions de traitement sur les modifications biochimiques et structurales du tissu musculaire ; une grande partie concerne le malaxage. Les essais relatifs au marinage ont permis de fixer le pH et la teneur en NaCl de petits échantillons de Semitendinosus de bœuf respectivement à 6,5, 5,4 ou 4,3 et à 0,9 ou 2 % en masse ; une ANOVA a révélé les effets de ces 2 paramètres sur la taille des cellules et des espaces extracellulaires, l’oxydation des lipides et des protéines et l’hydrophobie de surface de ces dernières. Un simulateur de saumurage-malaxage conçu par le laboratoire a permis d’imposer des successions de déformations contrôlées (nombre de 350 à 2500, taux de compression de 10 à 30%) à des muscles Semimembranosus (SM) ou Rectus femoris (RF) de porc. Des traitements mécaniques semblables à ceux existant dans des barattes industrielles de tailles différentes ont ainsi été reproduits. Les principales conclusions sont : (1) le malaxage augmente nettement la diffusivité apparente du NaCl, d’une part, en altérant la structure tissulaire (+ 20 %), et d’autre part, en induisant une convection s’ajoutant à la diffusion (+200 %) ; (2) le traitement mécanique entraine en lui-même une augmentation de la solubilité des protéines, connue pour moduler les qualités des viandes transformées, de 20 à 50% par rapport à des échantillons non malaxés, qu’ils soient salés ou non ; (3) il entraine aussi une augmentation modérée de l’hydrophobie des protéines ; (4) la dégradation de l’endomysium, servant d’indicateur des modifications structurales, est plus marquée au milieu qu’en périphérie du muscle malaxé et d’autant plus importante que le traitement mécanique est fort et long. / Marinating and brining improve shelf-life, tenderness and juiciness of meat and fish. As a supplement massaging or tumbling is often applied to meat pieces before cooking. The main aim of this study was to assess the impacts of the processing conditions on the biochemical and structural changes in the meat tissue; a great part is focused on massaging. In the marinating trials the pH and NaCl content of thin samples of beef Semimembranosus muscle were set at 6.5, 5.4 or 4.3 and at 0,9 or 2 % (w/w), respectively; an ANOVA have shown the effect of these two parameters on the cells and extra cellular space sizes, the oxidation of lipids and proteins and the protein surface hydrophobicity. A brining-massaging simulator built by the laboratory was used to apply controlled successions of deformations (number from 350 to 2500, compression ratio from 10 to 30 %) to Semimembranosus (SM) ou Rectus femoris (RF) pork muscles. Mechanical treatments similar to those existing in industrial tumblers of various diameters were so reproduced. The main conclusions are: (1) massaging clearly increases the NaCl apparent diffusivity, on the one hand, by a modifying the tissue structure (+20%) and, on the other hand, by adding convection to diffusion (+200%); (2) the mechanical treatment promotes by itself an increase in protein solubility, known to affect processed meat quality, from 20 to 50 % in comparison with salted or unsalted reference samples; (3) it also increases moderately protein hydrophobicity; (4) the endomysium degradation, used as an indicator of structural changes, was more pronounced in the muscle periphery than in the middle and all the more marked than massaging was strong and long.

Hydrodynamic multiplicity in the trickle flow, or low interaction, regime is a well documented phenomenon. Multiple hydrodynamic states are often presented in the form of hysteresis loops where the hydrodynamic parameter studied are shown as a function of the operating history of the bed, i.e. liquid and gas flow rates. In extreme cases the lower leg, representing an increase in liquid flow rate on a pre-wetted and drained bed, is commonly referred to as the Levec mode. The upper extreme, referred to as the Kan-liquid mode, represents a decrease in liquid flow rate after operation in the high interaction regime. The many reported studies investigating liquid-solid mass transfer in trickle beds have generally used either the dissolution or electrochemical techniques. Numerous researchers have used their data to develop correlations predicting solid-liquid mass transfer coefficients. Most of these studies do not specify the multiplicity mode of operation. Only two studies (Sims et al. (1993) and Van der Merwe, Nicol&Al-Dahhan (2008)) use both the Levec and Kan-liquid operating modes. Both of these studies suggest that solid-liquid mass transfer also exhibit multiplicity behaviour although the trends suggested or speculated differ from each other. Sims et al. (1993) found that a Kan-liquid operated bed will outperform a Levec operated bed; however in contrast to this Van der Merwe et al. (2008) speculated that a Levec operated bed is better suited for liquid limited reactions due to enhanced liquid-solid mass transfer in the Levec mode as a result of faster interstitial velocity. This study showed that solid-liquid mass transfer coefficients, measured with both the dissolution and electrochemical technique, show multiplicity behaviour. Two distinct operating regions were found, which corresponds to the Levec and Kan-liquid modes. Measurements taken using the electrochemical technique yielded solid-liquid mass transfer coefficients larger than those measured using the dissolution method. The experimental results agree with the trend found by Sims et al. (1993) but the mass transfer coefficients in this study were significantly lower. Additionally it was shown that the difference in mass transfer coefficients, in the two modes, cannot be explained by merely compensating for the differences in wetting efficiency and interstitial velocity, suggesting that the Levec mode has a larger percentage of stagnant or poorly irrigated zones. It was also shown that mass transfer coefficients measured at the top of the column is higher than those measured at the bottom, suggesting that the flow structure is changing as a function of axial length. Lastly, with regards to electrochemical measurements of liquid-solid mass transfer, it was shown that measurements using a single particle electrode compared well to that of a multiple packing electrode. / Dissertation (MEng)--University of Pretoria, 2009. / Chemical Engineering / unrestricted

Orientador: Maria Angela de Almeida Meireles / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-26T21:20:51Z (GMT). No. of bitstreams: 1 Jesus_SusanaPereirade_D.pdf: 19153904 bytes, checksum: e8d3e5239f2dbe5f9d61e1e553bad266 (MD5) Previous issue date: 2015 / Resumo: A extração supercrítica consiste em uma operação unitária de separação na qual o solvente é um fluido no estado supercrítico, sendo que o dióxido de carbono (CO2) é o mais utilizado. Destaca-se por ser reconhecida como uma tecnologia limpa, alternativa aos métodos convencionais que em geral utilizam solventes orgânicos prejudiciais à saúde e ao meio-ambiente. O processo de extração supercrítica tem sido extensivamente estudado pela comunidade científica há mais de três décadas, o que resultou na construção de um sólido conhecimento sobre os principais fundamentos envolvidos neste processo, além da formação de uma ampla base de dados para descrever o comportamento de diferentes sistemas (CO2 + matriz sólida). É uma técnica de extração a alta pressão que começou a ser utilizada em escala comercial na década de 1980 e, desde então, o número de plantas em operação é crescente em algumas regiões como Europa, Ásia e Estados Unidos. Apesar disso, continua a ser considerada uma tecnologia emergente e inovadora, visto que os métodos convencionais ainda são predominantes em diversas aplicações industriais e, em muitos países (como é o caso do Brasil), a técnica ainda não é utilizada em escala comercial. A viabilidade técnica do processo de extração supercrítica já está consolidada e a tecnologia encontra-se disponível comercialmente. Além disso, pesquisadores da área afirmam que a técnica pode ser economicamente competitiva, dependendo da área de aplicação e do produto de interesse. Entretanto, a questão econômica ainda é considerada como o principal empecilho à disseminação desta técnica, pois os custos de investimento associados a uma planta de alta pressão são altos quando comparados à instalação de plantas que operam em baixas pressões. Diante deste cenário, considera-se importante a investigação de métodos de cálculo (modelagem e simulação) que possam ser aplicados no sentido de estimar parâmetros para design de processo e aumento de escala, os quais são requeridos em estudos de viabilidade econômica. No presente trabalho, dados disponíveis na literatura foram utilizados para estudar a modelagem matemática da transferência de massa no processo de extração supercrítica. Para tanto, dados cinéticos de matérias-primas diversas foram ajustados por meio da aplicação de diferentes modelos, tendo como foco avaliar a versatilidade e aplicabilidade dos mesmos em termos de design de processo. Os resultados demonstraram que o modelo spline e o modelo de Sovová foram eficientes na descrição quantitativa da curva de extração, além de apresentarem versatilidade para ajustar curvas com formatos diferenciados. O modelo spline apresentou os melhores ajustes e também menores erros na descrição da etapa CER (Constant Extraction Rate), a qual é a mais importante em termos de design de processo / Abstract: Supercritical fluid extraction (SFE) is a solid-fluid separation technique in which the solvent is a fluid in the supercritical state, and the supercritical carbon dioxide (CO2) is the most used one. It is recognized as a green technology and a versatile alternative to conventional extraction methods, which generally use organic solvents that are harmful to human health and environment. The SFE process has been extensively studied by scientific community for more than three decades. As a consequence, a solid knowledge about the fundamental concepts has been developed, and there is a huge amount of data to describe the behavior of different systems (CO2 + solid matrix). It is a high-pressure extraction method that has been carried out on a commercial scale since the 1980s. From that point on, a growing number of industrial plants have been operating in Europe, Asia, and USA. However, SFE can still be considered an emerging technology since the conventional methods remain the most used in various applications. Besides, this technique has yet not been applied on a commercial scale in several countries, such as Brazil. The technical feasibility of SFE process is consolidated and the industrial-scale technology is commercially available. Researchers in this field claim that costs of SFE may be commercially competitive, depending on application area and target products. Nonetheless, the economic aspects are still considered an obstacle in SFE technology dissemination. This happens especially because a high pressure process requires higher investment costs than a conventional low pressure plant. In this scenario, it is important to investigate calculation methods (modeling and simulation) that may be applied to estimate parameters for process design and scale-up, which are key points in studies of economic viability. In this work, the mathematical modeling of SFE mass transfer was investigated by using experimental data from literature. Then, different models were applied to fit the kinetic data of SFE from various raw materials. The main purpose was to evaluate the models by considering their versatility and applicability in terms of process design. The results showed that spline and Sovová¿s models have been very effective in describing the quantitative behavior of the extraction curves. Moreover, these models presented versatility in fitting different curve shapes. The spline model provided the best fits as well as the lowest residual errors in the CER (Constant Extraction Rate) period, which is the most important region for process design purposes / Doutorado / Engenharia de Alimentos / Doutora em Engenharia de Alimentos

Orientador: Fernando Galembeck / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T09:01:49Z (GMT). No. of bitstreams: 1 Balestrin_LiaBeraldodaSilveira_M.pdf: 4255591 bytes, checksum: c4d0f9d5952dc35354bfb9f0d111643b (MD5) Previous issue date: 2015 / Resumo: Quando dois materiais isolantes são atritados, ocorre a triboeletrização de suas superfícies, isto é, a formação de cargas estáticas, distribuídas em padrões fractais. Uma das hipóteses para explicar a eletrização de isolantes é a ocorrência de reações mecanoquímicas seguidas da transferência mútua de massa. Esta dissertação apresenta mapas de potencial elétrico de superfícies atritadas, que também foram examinadas por microscopia eletrônica de varredura (SEI, BEI) e microanálise EDX. Os resultados verificam a hipótese mecanoquímica associada à transferência de fragmentos poliméricos iônicos, sendo as reações iniciadas pela quebra de cadeias seguida da formação de várias espécies de alta energia e produtos de oxidação. Microanálises também detectaram a fixação de N2 nestas superfícies, evidenciando a participação da atmosfera e a formação de triboplasma. As imagens BEI revelam uma distribuição fractal de composição química consistente com a distribuição de fragmentos limitada por difusão, mas superior à dimensão fractal de distribuição de cargas. Esta diferença é atribuída à supressão de cargas devido a microdescargas elétricas desencadeadas por gradientes superiores à rigidez dielétrica do sólido ou do ar. As microdescargas diminuem os gradientes elétricos, mas, ao mesmo tempo, geram novas espécies muito reativas, aumentando a heterogeneidade química das superfícies. Essa dissertação descreve também alguns experimentos acerca da eletrização produzida por simples contato, obtendo-se padrões bem definidos com tempo de contato de 1 h, porém não revelam a transferência de fragmentos poliméricos mutuamente, sugerindo que o cisalhamento desempenhe um papel importante na transferência de fragmentos poliméricos eletrizados. Em um menor grau de aprofundamento, esta dissertação contempla outras consequências de cargas estáticas, como alterações no coeficiente de atrito / Abstract: Triboelectrification occurs when two insulators are rubbed, i.e. static charges are formed on the surface with a fractal distribution pattern. One of the hypotheses raised by the literature indicates that the electrification is accompanied by mutual mass transfer. This dissertation presents electric potential maps of rubbed surfaces, which were also examined by scanning electron microscopy (SEI, BEI) and EDX microanalysis. The results verify the hypothesis that the electrification is due to mechanochemical reactions associated with transfer of charged polymeric fragments. The reaction is initiated by breaking the chains, generating reactive species and oxidation products. Microanalysis also detected N2 fixation on these surfaces, evidencing the contribution of the atmosphere and the formation of triboplasma. The BEI images show a fractal distribution of chemical composition consistent with a fragment distribution limited by diffusion, but higher than the fractal dimension of the charge distribution. This difference is attributed to the suppression of charges due to electrical micro discharge triggered by gradients higher than the dielectric strength of solid or air. The micro discharges decrease electrical gradients, but at the same time, generates very reactive species further increasing the chemical heterogeneity of surfaces. This dissertation also describes some experiments about the electrification produced by single contact, resulting in well-defined patterns with a contact time of 1 h, but do not show the mutual transfer of polymeric fragments, suggesting that the shearing plays an important role in transferring electrified fragments. This work also includes other consequences of static charges, such as changes in the friction coefficient / Mestrado / Físico-Química / Mestra em Química

The body of literature on the impact of emulsion particle size on oxidation rates is unclear. This could be because emulsions are typically polydisperse and the oxidation rate of individual droplets is impossible to discern. Flow cytometry is a technique for studying individual cells and their subpopulations using fluorescence technologies. It is possible that individual emulsion droplets could also be characterized by flow cytometry as a novel approach for studying lipid oxidation. Typical emulsion droplets are too small to be visualized by flow cytometer, so emulsions were prepared to have droplets > 2 μm; weighting agent and xanthan gum were added to minimize creaming during storage. A radical-sensitive lipid-soluble fluorescence probe (BODIPY665/676) was added to the lipid used to prepare the emulsion so that the susceptibility of individual emulsion droplets could be determined. The results showed that in a polydisperse emulsion system, small droplets were oxidized faster than large droplets. Using mixtures of emulsions with and without prooxidants, it was possible to see the transfer of prooxidants between droplets, a process that is influenced by surfactant and salt concentrations. For example, surfactants micelles can transfer prooxidants to neighboring non-oxidized droplets and cause fluorescence loss when surfactant concentration was higher than critical micelle concentration (CMC). Transfer of prooxidants was promoted by adding NaCl and free fatty acid which could be attributed to the lower CMC. This study showed the potential for applying flow cytometry on oxidation of individual emulsion droplets.

With the world’s increasing usage of electronic devices such as mobile devices and batteries, improving the reliability and performance of these devices has become more and more important. Besides the common overheating issues, low-temperature environments can also cause performance degradation or failure to these devices. Research on thermal switches and thermal regulators aims to improve the thermal management of electronic devices across a range of operating conditions. However, continuous tuning of thermal transport with all-solid-state systems is still challenging. The primary purpose of this work is to propose and demonstrate compressible foams as novel variable thermal resistors and thermal regulators to control device temperature under various input heat flux and ambient temperature. The graphene/PDMS foam is first tested in this work to demonstrate promising performance as a thermal regulator, with continuous tuning capability and a system switching ratio over ~4. Then, the dependence of the thermal conductivity of polymer foams during compression is studied, where the thermal conductivity is measured using a customized system based on an infrared microscope. Unexpectedly, the thermal conductivity decreases slightly at a compression level of more than 10x, in contrast to common theories that the thermal conductivity would increase with the mass density. A simple “spring model” is proposed as a limit where the ligaments do not build contacts during compression. Our results now fall in between the “spring model” and other common theories and can be explained. To gain further insights, a molecular dynamic simulation is performed on a graphene random nanofoam on the nanoscale. The result also shows that the effective thermal conductivity along the compression direction is not sensitive to the mass density, consistent with our experimental data on the macroscopic scale. This work provides useful insights into dynamic thermal management of electronic devices.

This dissertation focuses on studying membrane air dehumidification for a membrane moisture exchanger in a membrane heat pump system. The study has two parts: an optimization of membrane moisture exchanger for air dehumidification in the macroscale, and diffusion of water vapor in polymer nanocomposites membrane for humid air dehumidification in the nanoscale. In the first part of the research, the mass transport of water vapor molecules through hydrophilic silica nanochannel chains in hydrophobic polyurethane matrix was studied by simulations and experiments for different membrane moisture exchanger design configurations. The mass transport across the polymer nanocomposite membrane occurs with the diffusion of moist air water vapor molecules in the membrane moisture exchanger in a membrane heat pump air conditioning system for air dehumidification purposes. The hydrophobic polyurethane matrix containing the hydrophilic silica nanochannel chains membrane is responsible for transporting water vapor molecules from the feed side to the permeate side of the membrane without allowing air molecules to pass through.In the second part of the research, diffusion analysis of the polymer nanocomposite membrane were performed in the nanoscale for the polymer nanocomposite membrane. The diffusion phenomena through the polymer, the polymer nanocomposite without modifying the silica surfaces, and the polymer nanocomposite with two different silica modified surfaces were studied in order to obtain the highest water vapor removal through the membrane. Different membrane moisture exchanger configurations for optimal water vapor removal were compared to get the desired membrane moisture exchanger design using the finite element method (FEM) with the COMSOL Multiphysics software package. The prediction of mass transport through different membrane configurations can be done by obtaining the mass flux value for each configuration. An experimental setup of one membrane moisture exchanger design was introduced to verify the simulation results. Also, for different membrane structures, permeability was measured according to the ASTM E-96 method. The prediction of water vapor diffusion through the polymer nanocomposite was studied by molecular dynamics simulation with the MAPS 4.3 and LAMMPS software packages. As a new nanocomposite material used in air dehumidification application, water vapor diffusivity through Silica-Polyurethane nanocomposite membranes was measured by the random movement of water vapor molecules through the formed nanochannels in the nanocomposite. For the diffusivity value, the Einstein's relationship was employed for the movement of each single water vapor molecule during the simulation time for all suggested membranes. The results of the proposed research will contribute to enhancing the energy efficiency of air conditioning systems by choosing the membrane moisture exchanger configuration which maximizes water vapor removal while, at the same time, enhancing the silica surfaces with the desired surface modifier that will maximize diffusion through the membrane itself.

This diploma thesis deals with the separation process of air polutant on air scrubber. Absorption of carbon dioxide was carried out into 1 % solution of sodium hydroxide. Theoretical part is aimed at mass transportation, theory of absorption and examples of scrubbers. Experimental part focuses on some operating characteristics of scrubber and on optimisation of two-phase flow. The influence of hydrodynamic conditions on the absorption efficiency was found.