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Nowadays, there are various electrokinetic phenomena which are utilized in a wide range of applications, ranging from microfluidics and colloid and interface science to electrochemistry. However, even after 200 years of research on electrokinetic phenomena, there are still open questions with respect to fundamental understanding. The focus of this thesis is on three different phenomena, i.e., streaming potential, streaming current and electroosmosis. Hence, the thesis is divided in two parts: The first part focuses on the applicability of the classical Helmholtz-Smoluchowski theory on streaming potential and streaming current measurements of poly(methyl methacrylate) (PMMA) wafers, to infer the zeta potential of this substrate in contact with liquids of defined pH and ionic strength. In detail, we perform electrical impedance spectroscopy measurements to infer the electrical resistance in a PMMA microchannel and derive novel correlations for the electrokinetic characterization of the substrate. We conclude that convection can have a significant impact on the electrical double layer configuration which is reflected by changes in the surfaces conductivity. The second part of the thesis is concerned with electroosmotic flows in porous substrates where we develop a phenomenological correlation which is based on dimensional reasoning. A large set of experiments is carried out using a relatively simple and cost-effective setup including different sintered packed beds of borosilicate microspheres. A centre-of-mass model of the experimental setup allows for the interpretation of various effects. Streaming current measurements result in a correlation for the zeta potential of borosilicate depending on ionic strength and pH of the liquid. Finally, a quantitative expression for electroosmotic flow in packed beds of granular material is derived from the experiments. This correlation can be employed with other materials as well. / Thesis (Master, Chemical Engineering) -- Queen's University, 2014-06-11 10:58:11.557

Soil pollution in recent years has emerged as an issue of great environmental concern. Contamination of soil by improper disposal or spillage of petrochemicals and products containing petroleum hydrocarbons is one of such pollution cases highly reported. To remediate petroleum contaminated soil, A DC powered electrokinetic reactor was used with biosurfactants as an enhancement for the remediation process. To begin with, studies were made under voltage variations of 10 V and 30 V with an electrode spacing of 185 mm. Biosurfactant with its producing microbes and biosurfactant free cells were introduced in the soil chamber after which the reactor was left to run for 10 days under the electric field. The technology was able to achieve the highest oil recovery of 75.15 % from the soil in 96 hours at 30 V. With other factors remaining constant, the reactor was also operated under a constant voltage of 30 V with configurations of fixed electrodes spacings of 335 mm, 260 mm,185 mm and continuous approaching electrodes at 335 mm, 260 mm and 185 mm. The current in the electrolyte was highest with the least electrode distance of 185 mm. The increase in current led to a direct proportional increase in the electroosmotic flow towards the cathode leading to increased coalescence of the oil from the soil as compared to the other electrode distances. The analysis of the results showed reduction in the total carbon content in the soil with viable oil recovery rates for all the electrode distances with 185 mm being the most effective in both oil recovery and degradation. The reactor was further operated with amended biosurfactant concentrations of 28 g/L, 56 g/L and 84 g/L to enhance the recovery of oil from the soil and aid in biodegradation of the remaining oil by hydrocarbon degrading microbes. The highest oil recovery of 83.15 % was obtained with the biosurfactant concentration of 56 g/L showing that the hyper increase in concentration of the biosurfactants is not necessary to have an efficient process. In all experiments the microorganisms were able to survive under the electro-halo-thermal environment in the reactor and degraded the remaining hydrocarbons to acceptable amounts in the environment. The bacteria were however affected by the constantly changing pH in all experiments. The presence of biosurfactants was so significant in aiding oil recovery and increasing bioavailability of hydrocarbons to the microbes. Production of biosurfactants in the reactor followed up by kinetic suggestions of the processes in the bioelectrokinetic reactor should be studied in future. / Dissertation (MEng (Environmental Engineering))--University of Pretoria, 2019. / Chemical Engineering / MEng (Environmental Engineering) / Unrestricted

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The influence of microparticles on electroosmotic flow was investigated experimentally and numerically. Experiments were conducted using four different particle types of varying chemical composition, surface charge and polarity. Each particle type was tested at five different volume fractions ranging from 0.001 – 0.025. With a constant applied electric field, positively charged particles enhanced the electroosmotic flow by as much as 850%. The enhancement depended on particle composition, size and concentration. For negatively charged particles, the bulk electroosmotic flow was retarded with the largest reductions being 35%. This occurred for the greatest negative paricle concentration studied. A final experimental study utilizing a single volume fraction and particle type was conducted using microtube inner diameters of 100 – 300 micrometers. It was found that the effective electroosmotic mobility decreases with increasing microtube diameter. A numerical study of microparticle influenced electroosmotic flow was also conducted for positively and negatively charged particles. A Galilean transformation was employed in which the particles were held stationary. A moving wall model was utilized to account for the particle velocity and the wall-induced electroosmotic flow. The particle-induced electroosmotic flow was also accounted for. A range of particle velocities were imposed in order to study the flow physics for a range of potential flows. Scenarios were run for a single tube diameter of 100 micrometers and a single particle diameter of 1.7 micrometers. Volume fractions of 0.001, 0.0075 and 0.025 were tested for both positively and negatively charged particles. At least two particle charges were studied for each volume fraction and polarity. Comparisons of the trends in the numerical model are qualitatively compared with the trends in the experimental data. The numerical and experimental data demonstrated similar trends. For positively charged particles, an increase in volume fraction showed a nonlinear increase in the average bulk flow velocity. For negatively charged particles an increase in volume fraction showed a nonlinear decrease in the average bulk flow velocity.

A further understanding of colloidal mixture behavior under applied electric fields would greatly benefit the design of smart material systems such as electrorheological fluidic devices and microfluidic reconfigurable antennas. This thesis presents a finite element analysis of colloidal mixture electrokinetic behavior. Computations of particle forces as a function of applied frequency and particle shape were performed. An effective medium property method was also studied. Fluidic and electric forces were obtained with various applied excitation frequencies throughout three locations in a coplanar microelectrode domain. This domain consists of two 50 nanometers thick gold electrodes separated by a 30 micrometers gap. The three locations are 1.2 micrometers, 40 micrometers, and 90 micrometers from the gap center. Total force vectors were computed by integrating Maxwell and Cauchy stress tensors to determine whether the particles are pushed toward or away from the electrode gap at frequencies of 10 Hz, 1 kHz, and 100 kHz. It was determined that particles were pushed outside the gap at median frequencies of 1kHz (indicating ac electroosmotic force domination) and began to be pushed back toward the gap at higher frequencies of 100 kHz (indicating dielectrophoretic force intensification). Particle shape effects were examined by calculating the electrical interparticle force between two particles at various incidences with respect to a uniform electric field. Particle attraction occurs when the line between the particle centers is aligned with the electric field; repulsion occurs when this center line is perpendicular. The incidence angle at which the particles switch from attraction to repulsion is defined as θcr. The aspect ratio and particle edge separation distances used in this study were 1, 5,12.92 and 0.25 micrometers, 0.50 micrometers, 2.0 micrometers, respectively. The results indicate that higher aspect ratio particles tend to have smaller θcr values and larger interparticle force magnitudes for given separation distances. Finally, effective dielectric constant simulations utilizing periodic crystalline arrangements of colloidal structure were performed. The results show good agreement with the Maxwell Garnett mixing rule at volume fractions above 30 percent. Less canonical structures of cubic particles were also modeled.

No description available.

Electrokinetically Driven Mixing in a Microchamber for Lab-on-a-Chip Applications Narayan Sundaram Abstract Micro-Total-Analysis-Systems (μTAS) have been the focus of recent world wide research due to their varied applications. Much of the motivation for the development of μTAS stems from applications in biotechnology and biomedicine. A typical μTAS device includes a number of functional units ranging from sample injection or ingestion, pre-concentration, mixing with reagents, chemical reactions, separation, detection, and possibly a chemical response. Mixing of constituents is one of the key functions desired of these systems for conducting analyses in a short span of time. The flow regime in these small devices (typical sizes 100μm) being predominantly laminar (Reynolds number, Re < 1), it becomes difficult to rapidly mix the constituent species. Hence for effective mixing, it is necessary to increase the Reynolds number and/or induce bulk motion such that the material interface between the components to be mixed is continously augmented. The method developed to induce such motion is by the application of an AC fluctuating potential field across a microchamber in which mixing is to be performed. The externally applied electric field applies a force on free ions in the charged Debye layer very close to the surface (1-10 nanometers) and induces a flow velocity which is proportional to the electric field. This applied fluctuating electric field gives rise to hydrodynamic instabilities which are responsible for increasing the material contact surface and hence augmenting the rate of mixing by an order of magnitude or more over pure diffusion. To further enhance mixing, microbaffles are strategically placed inside the microchamber and the mixing time was further decreased by a factor of two. Mixing was also studied in a neutral (no charge on the walls) microchamber. It was found that the mixing achieved in the absence of surface charge was comparable to the mixing achieved in the case with microbaffles. This work establishes that CFD is a useful tool that is capable of providing insight into the flow physics in devices with very small length scales. / Master of Science

O tratamento por técnicas eletroquímicas é provavelmente uma das metodologias mais prometedoras na descontaminação de sistemas particulados, sendo capaz da remoção, total ou parcial, de contaminantes como metais pesados, radionuclídeos, orgânicos e inorgânicos. Pelo uso de uma diferença de potencial elétrico em correntes baixas aplicadas através de pares de eletrodos, os contaminantes são movidos sob a ação do campo elétrico. A extração de impurezas pelo método eletrocinético é baseada na suposição que as moléculas estejam ou sejam evoluídos para a fase liquida. O ciclo completo envolve a adsorção, o transporte, a captação, e a remoção do contaminante dos meios porosos. Neste trabalho avaliou-se o emprego da técnica de eletroosmose na remoção de fenol em meios líquidos e porosos. O fenol foi escolhido por ser um composto altamente tóxico, proveniente de refinarias de óleos, industrias de tintas e principalmente pesticidas. Para a validação do processo em escala de laboratório, foi confeccionada uma célula eletroquímica para um volume de 700 cm3, com eletrodos de titânio. A concentração de fenol utilizada para este experimento foi constante de 11 mM. Água destilada, areia, pós de vidro e solo foram classificados, caracterizados e selecionados como meios porosos experimentais. As aplicações das cargas variaram de O a 120-140-240 minutos, sendo que o mapeamento do pH indicou eletromigração de espécies em todos os sistemas. Na eletroosmose temos o arraste das moléculas de fenol em direção ao catodo simultâneo à eletrólise da água, cujas concentrações relativas de contaminante foram avaliadas por espectroscopia de UV-Vis. A montagem dispõe de um reservatório para coleta de produtos de reação em cada eletrodo sendo possível a remoção do íon fenólico migrado. O processo apresentou eficiências variando de 40% a 60% na extração, dependendo das características do meio poroso. De um modo geral a técnica apresentou-se ecologicamente viável e econômica, como procedimento de remediação de solos e sistemas particulados diversos. / The use of electrochemical techniques is probably one of most promising technology for particulate system decontamination treatments. This methodology appears as able to remove heavy metals, radionucletides and organic and inorganic contaminations. By using an electric potential difference with low currents intensities through electrodes, the contaminants in the porous medium are dragged under electric field action. The contaminant removal is base on the supposition that the impurities are in solution or elute to the liquid phase. The whole cycle involves adsorption, transport, collection and removal of contaminants from the medium. In this work it was studied the use of the electroosmosis technique for removal of phenol from porous and aqueous medium. Phenol was chose because of its high toxicity and the regularly use in oil refineries, ink industries and pesticides. To validate the process, in laboratorial scale, an electrochemical cell of 700 cm3 volume, with titanium electrodes was constructed. The phenol concentration was 11 mM. Distillated water, sand, glass powder and sample of soil were classified, characterized and selected to constitute the porous media. The charge application time varied from 120 to 140 to 240 minutes and the pH mapping showed migration effect in ali of the systems. In the electroosmosis process we have the molecules of phenol dragged towards the cathode simultaneously to the water electrolysis. The relative concentrations of phenol were evaluated by UV-Vis spectroscopy. In the experimental setup a reservoir in each electrode was assembled in order to collect the reaction products. The process efficiencies are in a range from 40% to 60%, dependent of the porous medium characteristics. In a broad sense, the technique showed feasible as an economic and ecological procedure for soil and particulate system remediation.

O tratamento por técnicas eletroquímicas é provavelmente uma das metodologias mais prometedoras na descontaminação de sistemas particulados, sendo capaz da remoção, total ou parcial, de contaminantes como metais pesados, radionuclídeos, orgânicos e inorgânicos. Pelo uso de uma diferença de potencial elétrico em correntes baixas aplicadas através de pares de eletrodos, os contaminantes são movidos sob a ação do campo elétrico. A extração de impurezas pelo método eletrocinético é baseada na suposição que as moléculas estejam ou sejam evoluídos para a fase liquida. O ciclo completo envolve a adsorção, o transporte, a captação, e a remoção do contaminante dos meios porosos. Neste trabalho avaliou-se o emprego da técnica de eletroosmose na remoção de fenol em meios líquidos e porosos. O fenol foi escolhido por ser um composto altamente tóxico, proveniente de refinarias de óleos, industrias de tintas e principalmente pesticidas. Para a validação do processo em escala de laboratório, foi confeccionada uma célula eletroquímica para um volume de 700 cm3, com eletrodos de titânio. A concentração de fenol utilizada para este experimento foi constante de 11 mM. Água destilada, areia, pós de vidro e solo foram classificados, caracterizados e selecionados como meios porosos experimentais. As aplicações das cargas variaram de O a 120-140-240 minutos, sendo que o mapeamento do pH indicou eletromigração de espécies em todos os sistemas. Na eletroosmose temos o arraste das moléculas de fenol em direção ao catodo simultâneo à eletrólise da água, cujas concentrações relativas de contaminante foram avaliadas por espectroscopia de UV-Vis. A montagem dispõe de um reservatório para coleta de produtos de reação em cada eletrodo sendo possível a remoção do íon fenólico migrado. O processo apresentou eficiências variando de 40% a 60% na extração, dependendo das características do meio poroso. De um modo geral a técnica apresentou-se ecologicamente viável e econômica, como procedimento de remediação de solos e sistemas particulados diversos. / The use of electrochemical techniques is probably one of most promising technology for particulate system decontamination treatments. This methodology appears as able to remove heavy metals, radionucletides and organic and inorganic contaminations. By using an electric potential difference with low currents intensities through electrodes, the contaminants in the porous medium are dragged under electric field action. The contaminant removal is base on the supposition that the impurities are in solution or elute to the liquid phase. The whole cycle involves adsorption, transport, collection and removal of contaminants from the medium. In this work it was studied the use of the electroosmosis technique for removal of phenol from porous and aqueous medium. Phenol was chose because of its high toxicity and the regularly use in oil refineries, ink industries and pesticides. To validate the process, in laboratorial scale, an electrochemical cell of 700 cm3 volume, with titanium electrodes was constructed. The phenol concentration was 11 mM. Distillated water, sand, glass powder and sample of soil were classified, characterized and selected to constitute the porous media. The charge application time varied from 120 to 140 to 240 minutes and the pH mapping showed migration effect in ali of the systems. In the electroosmosis process we have the molecules of phenol dragged towards the cathode simultaneously to the water electrolysis. The relative concentrations of phenol were evaluated by UV-Vis spectroscopy. In the experimental setup a reservoir in each electrode was assembled in order to collect the reaction products. The process efficiencies are in a range from 40% to 60%, dependent of the porous medium characteristics. In a broad sense, the technique showed feasible as an economic and ecological procedure for soil and particulate system remediation.