Theoretical models for the electrokinetics of weakly permeable porous colloidal particles are absent from the literature. The understanding of this topic will be advanced through a systematic analysis of the standard electrokinetic equations, resulting in a theory for the electrophoretic mobility of weakly permeable porous colloidal particles. / The standard electrokinetic equations are employed to model the flux of solvent and ions outside the porous particle. To be consistent with this approach, the flux of solvent and ions in the pores must also be governed by the standard electrokinetic equations. However, in practice, only transport phenomena on the particle scale are observed and it is sufficient for information regarding pore-scale behaviour to be retained purely in the form of averaged quantities. To complete the theoretical description, the standard electrokinetic equations outside the particle must be coupled to particle-scale transport equations inside the particle via boundary conditions at the porous/free-fluid interface. / It has been shown experimentally and theoretically for coupled Stokes and Darcy flows, that the correct interfacial boundary condition for the tangential external flow is given by the Beavers-Joseph-Saffman (BJS) condition. The effect of the BJS boundary condition on the hydrodynamic drag on an oscillating porous particle is investigated. It is found that the particle may be regarded as impermeable with a slip length independent of frequency, and the resulting drag is significantly reduced in comparison with an equivalent impermeable particle that does not exhibit a slip length. / The transport of a general electrolyte solution through a rigid porous body subjected to a static (d.c.) electric field is studied. The pore-scale description is given by the standard electrokinetic equations, including the effects of ion diffusion, electromigration and convection. Homogenization theory is used to derive transport equations that capture the particle-scale behaviour. It is proven that the transport coefficient tensors obey Onsager’s reciprocal relations and the diagonal coefficient tensors are positive definite. / New interfacial boundary conditions are derived using conservation arguments supplemented by Stern-layer theory. When combined with the particle-scale transport equations, these boundary conditions incorporate four principal effects into the standard electrokinetic model: solvent slip and Stern-layer ionic conduction at the interface, and macroscopic ionic conduction together with the electroosmotic flow of solvent through the particle. / The method of matched asymptotic expansions is then used to construct an approximate solution to the aforementioned system, in the thin double-layer limit. An expression for the electrophoretic mobility of a weakly permeable colloidal sphere is produced that consists of a generalization of Smoluchowski’s formula to encompass porous particles, and a next order correction. For the first time, the effects of solvent slip and Stern-layer ionic conduction within the porous/free-fluid interface, in conjunction with macroscopic ionic conduction and electroosmosis through the particle, are exhibited. It is shown that solvent slip at the porous interface is overwhelmingly the dominant effect on the mobility of weakly permeable porous colloidal particles.

Les performances et la durée de vie des piles à combustible à membrane échangeuse de protons (PEMFC) dépendent fortement de la répartition de l'eau dans les assemblages membrane électrodes (AME). Une répartition d'eau homogène et suffisante s'avère indispensable pour obtenir de bonnes performances et une grande durabilité. Fondamentalement, la répartition d'eau dans l'AME, et plus particulièrement dans la membrane, est déterminée par deux mécanismes de transport d'eau : le flux d'électroosmose, induit par les protons véhiculant les molécules d'eau de l'anode vers la cathode, et le flux de diffusion d'eau, de la cathode vers l'anode, résultant du gradient de concentration. Or, ces mécanismes sont pour l'heure encore mal connus malgré les intenses recherches menées sur le sujet. Dans ce contexte, la première partie de cette étude s'appuie sur la détermination et la quantification des mécanismes de transport d'eau dans les différents composants, et notamment dans les membranes, ainsi que sur l'étude de leur couplage. Ces propriétés ont été évaluées en fonction du degré d'hydratation et de la température à l'aide de deux méthodes originales développées dans cette thèse. Afin d'homogénéiser la répartition d'eau, et ainsi d'améliorer les performances des PEMFC, le développement d'une nouvelle structure de membrane à gradient de masse équivalente a fait l'objet de la deuxième partie de l'étude. Cette nouvelle structure membrane a été étudiée par la caractérisation de ses propriétés du transport d'eau, par la détermination de la répartition d'eau ex et in-situ par spectroscopie Raman confocale ainsi que par des tests électrochimiques. Les performances électrochimiques ont été corrélées aux propriétés de transport d'eau, selon l'orientation du gradient de masse équivalente de la membrane par rapport au sens des protons. Nous avons ainsi démontré qu'il est possible de modifier la répartition d'eau et les performances en modifiant le sens de la structure de la membrane par rapport aux réactions électrochimiques. / Water management is a fundamental issue for the improvement of the PEMFC technology. The cell performances and life time depend strongly on the water repartition in the Membrane Electrodes Assembly (MEA). This water repartition within the MEA is mainly governed by two flows across the membrane : electroosmosis, which drags water molecules from the anode to the cathode and often leads to local depletion of water in the membrane at the anode side ; back diffusion (from cathodeto anode) induced by the water concentration gradient generated from the water produced at the cathode side, which allows to hydrate the membrane and the anode. For nowadays, these phenomena are still under debate in spite of numerous researches. In this context, this work is firstly focused on the determination and the quantification of the mechanisms of water transport in different components, particularly in the membranes, as well as their coupling thanks to two original methods developed in this work. In the aim to achieve a more homogeneous water repartition, and consequently to improve the cell performance, a new membrane structure based on an inner gradient of equivalent weight has been fabricated. Its water transport properties, the cell performance, and the ex and in-situ water repartition have been characterised. A consistent relationship between the performance and the membrane water transport properties have been established depending on the direction of the gradient of equivalent weight compared to the protons flow.

Bioavailability denotes the ‘degree of interaction of chemicals with living organisms’. High bioavailability is generally needed for efficient biodegradation of environmental contaminants. Therefore, technologies to promote contaminant availability should foster bacterial transport and/or control interactions of chemicals with environmental matrices. Direct current (DC) electric fields and their electrokinetic phenomena (electro-migration, electroosmosis, and electrophoresis) have the potential to promote contaminant bioavailability by both mobilizing bacteria and contaminants. This thesis hence tested electrokinetic factors affecting bacterial transport and deposition and the interactions of contaminants with geo-sorbents, respectively. Studying electrokinetic effects on bacterial transport, we found that DC fields significantly changed bacterial deposition during transport in percolated laboratory columns. By calculating the bacteria collector interaction force FDLVO, the electroosmotic shear force FEOF, the electrophoretic drag force FEP, and the hydraulic shear force FHF, we developed an approach that interlinked the net forces Fnet on a bacterium to observed deposition efficiencies. The driving factor of electrokinetic effects was found to be the relative strength of |FEOF| and |FEP|. If |FEOF| > |FEP|, increased bacterial deposition efficiency and if |FEOF| < |FEP| decreased bacterial deposition efficiency was predicted. Investigating electrokinetic effects on bacterial deposition on planar surfaces using quartz crystal microbalance with dissipation (QCM-D) we confirmed our model by using different bacteria at varying ionic strengths of the electrolyte and of the DC electric applied, respectively. Our model can be used to predict DC field effects on bacterial deposition. Investigating the electrokinetic effects on the sorption/desorption of the model polycyclic aromatic hydrocarbon contaminant phenanthrene (PHE) we found that DC fields changed the rates and extents of PHE sorption and desorption in all geo-sorbents. Matrices of varying sorption strengths were tested. In strongly sorbing carbonaceous sorbents, the electroosmotic flow (EOF) increased the rates of PHE sorption and reduced PHE desorption while in more weakly sorbing matrices, EOF significantly reduced PHE sorption and increased its desorption. By interlinking the Gibbs free energy change of sorption (ΔGº) and the EOF velocity, an approach was developed to estimate electrokinetic effects on the sorption and desorption of PHE. The results of this thesis propose that electrokinetic phenomena have significant impact on both freely dissolved contaminant concentrations and bacterial deposition in porous media. They hence have high effect on contaminant bioavailability. Using conceptual approaches interlinking the electrokinetic forces with ΔGº and bacteria-matrix interactions energies (GDLVO), respectively, we were able to estimate electrokinetic effects on bacterial deposition and contaminant release. Our data thus give rise to future technical applications to control the bioavailability in natural and manmade ecosystems.

No description available.

This thesis describes the use of chiral counter-ions for the enantiomeric separation of amines in non-aqueous capillary electrophoresis. The investigations have been concentrated on studies of the influence, of the chiral counter-ion, the solvent, the electrolyte and the analyte, on the enantioselective separation. Modified divalent dipeptides have been introduced in capillary electrophoresis for the separation of amino alcohols and chiral resolution of amines. Association constants for the ion-pair between dipeptide and amino alcohol could be utilized for development of separation systems with higher amino alcohol selectivity. Chiral discrimination (ion-pair formation) between the dipeptides and amines are preferably generated in non-aqueous background electrolytes (BGEs). The amount of triethylamine in the BGE determined the dipeptide charge and a divalent dipeptide promoted higher enantioselectivity than a monovalent dipeptide. An N-terminal-end blocking group and glutamic acid at the C-terminal-end of the dipeptide was important for chiral separation of the amines. Chemometric and univariate methods have been employed for evaluation of suitable solvent compositions in the BGE. An experimental design including a single solvent as well as binary, ternary and quaternary mixtures of polar organic solvents, showed that optimal enantioresolution was obtained with an ethanol:methanol 80:20 mixture in the BGE.  Furthermore, water was found to have an adverse influence on enantioselectivity and no enantioresolution was obtained with BGEs containing more than 30 % water. An alkali metal hydroxide added to the BGE affected the chiral separation by competing ion-pair formation with the selector. The electroosmosis was reduced in order of decreasing alkali metal ion solvated radius and became anodic using K, Rb or Cs in ethanolic BGEs. The correlation between the amino alcohol structure and the enantioselectivity was investigated using chemometrics. The obtained models showed that enantioselectivity for the amino alcohols was promoted by e.g. degree of substitution and substituent size on the nitrogen.

CNT membrane platforms are biomimetic polymeric membranes imbedded with carbon nanotubes which show fast fluid flow, electric conductivity, and the ability to be grafted with chemistry. A novel micro-dialysis probe nicotine concentration sampling technique was proposed and proved in vitro, which could greatly improve the efficiency and accuracy of future animal transdermal studies. To enhance the scope of transdermal drug delivery which was limited to passive diffusion of small, potent lipophilic drugs, a wire mesh lateral electroporation design was also proposed which could periodically disrupt the skin barrier and enhance drug flux. It was shown that AMP binding aptamer at the tip of carbon nanotubes may act as gatekeepers and regulate ionic transport through CNT membrane. Multiple cycle gating of ionic transport upon AMP binding/unbinding which changes the aptamer conformation was displayed. This CNT membrane-aptamer system closely mimics how protein ion channels modulate ion flow by responding to stimuli, which may have significant impact on active membrane transport. Finally an enhanced electroosmosis concept by “ratchet” functionalization at both ends of carbon nanotubes in was discussed. Direct observation of water transport by electroosmosis was made possible through enhanced flow in vertically aligned high flux CNT membranes.

Varje år i Sverige sker ca 24 000 skallskador på grund av yttre trauma och 30 000 strokeskador. Ett betydande antal får sekundära skador på grund av den ökade vattenhalten kring den skadade hjärnvävnaden. Föreslagen metod är att inducera vattenflöde från skadad till frisk vävnad baserat på teorin om elektroosmotiskt flöde. Teorin bakom elektroosmotiskt flöde är att ett flöde induceras då en spänning läggs över ett medium. Elektroosmotiskt flöde tillämpas i industrin och kallas då electro-osmotic dewatering (EOD). Tekniken används för avvattning av biomaterial, leror, tofu ark samt inom tumörbehandling. I arbetet har utförts flera experiment på hjärnfantomer av agarosgel för att undersöka om metoden kan användas för att leda bort vatten. Första experimentet gjordes för att bevisa att ett flöde induceras vid pålagd spänning över fantom. Andra experimentet undersöker förhållandet mellan flödet, spänningen och strömmen. Resultatet blev linjära förhållanden mellan flödet och spänningen, flödet och strömmen samt mellan spänningen och strömmen. Med litteraturkällor och experimentella resultat härleddes ett samband för att kunna bestämma flödet vid pålagt elektriskt fält. Arbetet avslutades med litteraturstudie i elektrodens material, utformning och placering. Rekommendationerna blev att använda platta elektroder med en strömtäthet under 25 mA/m2. Placeringen optimeras genom förbestämda Finite Element (FE) simuleringar av typskador. / Every year in Sweden there is about 24,000 head injuries due to external trauma and 30,000 strokes. A significant number may develop secondary damage because of the increased water content around the damaged brain tissue. The proposed method is to induce water flow from damaged to healthy tissue based on the theory of electroosmosis. The theory behind the electroosmosis is that a flow is induced when a voltage is applied across a medium. The theory of electroosmosis is applied in industry and called electro-osmotic dewatering (EOD) which is used as a drying technique for the dewatering of bio-materials, clays, tofu sheets and electroosmosis is also applied in clinical treatment of tumors. Several experiments were performed on brain phantoms consisting of agarose gel to examine whether the method can be used to divert water. The first experiment was done prove that a flow can be induced when a voltage is applied over the phantom. The second experiment was to investigate the relationship between the flow rate, voltage and current. The result showed linear correlation between flow rate and voltage, flow rate and current, and between the voltage and current. The literature sources and experimental results were referred to a relationship which is developed to determine the flow induced by electrical field. The work was completed with recommendations in electrode material, design and placement. The recommendations are to use plate electrodes at a current density under 25 mA/m2. Electrode placement is predetermined by Finite Element (FE) simulations of different types of injuries.

No description available.

No description available.

Made available in DSpace on 2015-03-26T13:27:45Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1452427 bytes, checksum: ad89ed1f2acb1864018bdd4b54b3fc9e (MD5) Previous issue date: 2008-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This research addressed the application of electrokinetic phenomena in soil remediation, considering the application of electroosmosis in the decontamination of three soils from the Zona da Mata Norte, Minas Gerais state, Brazil, contaminated with the element-trace cadmium. This work followed a line of research previously developed at the Universidade Federal de Viçosa, including the evaluation of the electroosmotic process in the chemical and mineralogical parameters of a larger gamma of soils, as well as evaluating the effect of testing parameters in the efficiency of the decontamination process. The tested soils were residual products from gneiss, as follow: (i) soil 1, a mature residual soil, pedologically classified as Red Yellow Latosol, presenting lateritic geotechnical behavior and silty-sandy-clayey texture; (ii) soil 2, saprolitic, presenting non lateritic geotechnical behavior and clayey-silty-sandy texture; e (iii) soil 3, also a mature residual soil, pedologically classified as Red yellow Podzol (Argisol), presenting non- lateritic geotechnical behavior and sandy-siltyclayey texture. Cadmium was the element- trace used in the experiment because it is a usual polluting source in daily use objects and presents adsorption-desorption intermediate behavior. The study program was directed to the analysis of soil behavior before and after their contamination with cadmium, encompassing the following steps: (i) X-rays analysis; (ii) physical and chemical routine tests; (iii) determination of CEC and ZPC; (iv) evaluation of the influence of the applied compaction effort and, therefore, of structure, in the soils eletrosmotic conductivity coefficient; (v) evaluation of the influence of the applied electrical potential difference (ddp) of 5, 15 and 30 V in the electrokinetic decontamination process; (vi) analysis of the influence of the contaminant incubation time (periods of 1, 10 and 20 days) and of ddp (5, 15 and 30 V) in the decontamination process. The results had shown that: (i) quartz predominated in the soils sand fraction, whereas kaolinite predominated in the soils silt and clay fractions; however, it was observed significant presence of hematite and gibbsite in the clay fraction of soil 1 and of goethite in the clay fraction of soil 3; (ii) electrochemically, soils 1 and 3 revealed more active behavior, presenting higher specific cation adsorption capacity; (iii) the parameter ZPC was a determinant factor in all the analyzed soils chemical properties, as well as in the electrokinetic decontamination process, governing the direction of the eletrosmotic flow and influencing in the results of the decontamination applied technique; (iv) the addition of the contaminant to soils was responsible for significant changes in the routine analysis and in the CEC and ZPC parameters, specially regarding soils 1 and 3, which are the most active ones; (v) except for soil 3, the values of the electroosmotic conductivity coefficient of soil was not significantly influenced by the application of different electric potentials and different compaction efforts; (vi) for all tested soils, cadmium soils removal through electrokinetic phenomena increased significantly with the increase of the incubation time and with the increase of the applied electric potential difference. / O presente trabalho abordou a aplicação de fenômenos eletrocinéticos na remediação de solos, com um direcionamento ao emprego da eletrosmose na descontaminação de três solos da Zona da Mata Norte, estado de Minas Gerais, Brasil, contaminados com o elemento- traço cádmio. Buscou-se ampliar o horizonte de pesquisas já desenvolvidas na Universidade Federal de Viçosa, com a inclusão da avaliação do processo eletrosmótico em parâmetros químicos e mineralógicos de uma gama maior de solos, bem como avaliar o efeito de diferentes vairáveis na eficiência do processo de descontaminação. Trabalhou-se com solos residuais de gnaisse, como se segue: (i) solo 1, um residual maduro, pedologicamente classificado como Latossolo Vermelho-Amarelo, de comportamento geotécnico laterítico e textura argilo-areno-siltosa; (ii) solo 2, saprolítico, de comportamento geotécnico não laterítico e textura areno- silto-argilosa; e (iii) solo 3, também, residual maduro, pedologicamente classificado como Argissolo Vermelho- Amarelo, de comportamento geotécnico não laterítico e textura argilo-areno-siltosa. O elemento-traço empregado foi o cádmio, fonte poluidora presente em objetos de uso diário e que apresenta comportamento adsorção-dessorção intermediário. O programa de estudo foi dirigido aos solos antes e após contaminação com cádmio e abrangeu a realização de: (i) análises de difração de raios-X; (ii) análises de laboratório para determinação de propriedades física e química; (iii) determinações de CTC e PCZ; (iv) avaliação da influência da energia de compactação e, portanto, da estrutura, no coeficiente de condutividade eletrosmótica dos solos; (v) avaliação da influência da diferença de potencial elétrico aplicado (ddp) no processo de descontaminação eletrocinética, trabalhando-se com valores de 5, 15 e 30 V; (vi) análise da influência do tempo de incubação do contaminante (períodos de 1, 10 e 20 dias) e da ddp (5, 15 e 30 V) na descontaminação dos solos. Os resultados mostraram que: (i) na fração areia dos solos estudados, havia predomínio de quartzo, enquanto que nas frações argila e silte, havia dominância de caulinita; no entanto, observou-se presença expressiva de hematita e gibbsita, no solo 1, e de goethita, no solo 3; (ii) os solos 1 e 3, do ponto de vista eletroquímico e ambiental, mostraram-se mais ativos, podendo apresentar alta adsorção específica de cátions; (iii) o PCZ foi um fator determinante em todas as propriedades dos solos estudados, bem como no processo de descontaminação eletrocinética, mostrando-se associado o sentido do fluxo eletrosmótico aos resultados dos ensaios de descontaminação; (iv) a adição do contaminante aos solos produziu variações significativas nos seus parâmetros químicos obtidos via análises de rotina, CTC e PCZ, em especial no caso dos solos 1 e 3, mais ativos; (v) os valores do coeficiente de condutividade eletrosmótica não variaram significativamente com a aplicação de diferentes potenciais elétricos e de diferentes energias de compactação, exceto para o solo 3, provavelmente devido a fatores mineralógicos dos solos; (vi) a remoção de cádmio dos solos, através dos fenômenos eletrocinéticos, aumentou significativamente com o aumento do período de incubação e com o aumento da diferença de potencial elétrico aplicado, para todos os solos estudados.