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

An investigation into the parameters that define a good anchor block for a copolymer steric stabilizer was performed. The study focused on the effects of different functional groups on the adsorption properties of polymers. In addition, the effect of chain architecture as well as the impact of a hydrophobic end-group on polymer adsorption properties was determined. To complement the adsorption studies, a streaming potential instrument was built for use in measuring the adsorbed layer thickness of nonionic polymers on SiO₂. The research concluded with an examination of the effect of thermally induced insolubility on adsorption of a hydrogen-bonding polymer. Functional group effects were studied by measuring the adsorption isotherms of poly(2-ethyl-2-oxazoline), PEOX, poly(ethylene oxide), PEO, poly(vinyl alcohol), PVOH, and poly(ethylene imine), PEI, which was modified such that a 1,3-butanediol substituent replaced its imine hydrogens, on SiO₂, TiO₂, and Al₂O₃. PEOX and PEO, relatively basic polymers compared to PVOH were observed to adsorb only on the most acidic metal oxide, SiO₂. PVOH, however, was observed to adsorb on all three metal oxides, but to a lesser degree on SiO2 as compared to the more basic PEOX and PEO. These initial results were indicative of hydrogen-bonding mechanisms, a form of acid-base interaction. The most significant observation in the adsorption studies was that the linear hydroxyl modified PEI materials and their dendritic analogs adsorb on the metal oxides both above and below the i.e.p. This indicates that both electrostatic and hydogen-bonding mechanisms are driving the adsorption. The dendritic polymers, particularly a 4th generation dendrimer based on diaminopropane with a molecular weight of 16,640 g/mol adsorbed at a higher level when compared to the 41.3K g/mol PVOH and 30K g/mol PEOX. In addition to the dual adsorption mechanism, it was determined that the dendritic architecture appears to facilitate adsorption, as does the presence of the hydrophobic endgroup. The level of adsorption for all of the hydroxyl containing linear PEI and dendritic materials on the three metal oxides was high enough for them to be considered as anchor blocks in a copolymer steric stabilizer. The streaming potential instrument used to measure the adsorbed layer thickness on SiO₂. Adsorbed layer thickness of PEOX Mw = 10K and 30K g/mol were measured at approximately 1nm and 4.4 nm, respectively. In the case of the PEOX Mw = 30K g/mol homopolymer, the measured layer thickness was higher than that for a 23K g/mol PEO homopolymer. The degree of polymerization of the PEO is approximately 525, while for the PEOX it was only 300. This result was not expected. Finally, adsorption of PEOX was studied at the cloud point to determine whether insolubility could promote adsorption, while hydrogen-bonding, the room temperature driving force for adsorption, would decrease. Adsorption isotherm measurements were performed at 72 °C, and 75 °C, as the cloud point of the 30K PEOX was determined to be 73 °C. It was apparent that the adsorption decreased as temperature increased, indicating that without hydrogen bonding, thermally induced insolubility does not drive adsorption. / Ph. D.

This work deals with the development of a new label-free detection technique called Pulsed Streaming Potential (PSP). Its novelty relies on the adaptation of a classical electrokinetic phenomenon (streaming potential) into a tool which can evaluate molecular interplay in label-free fashion. Implementation of PSP to microfluidic platforms allowed the label-free sensing of binding events to plastic (modified and unmodified) surfaces. It was demonstrated the use of real time PSP in plastic microfluidic platforms for determination of kinetic parameters of the interaction of proteins and plastic surfaces. Moreover, initial change of PSP after adsorption of proteins showed to be proportional to the bulk concentration of proteins and it was used for quantification of Lysozyme in the nanomolar range. Several approaches were studied to manipulate the surface of microfluidic channels in order to improve selectivity of PSP through reduction of non-specific adsorption. These approaches included the fabrication of composite surface of polyacrilic acid (PAA) and polyethylene glycol acrylate (PEGA) on cyclic olefin copolymer microchannels, as well as adsorption of nanospheres on COC-PEGA channels.

Inkjet printing has generated considerable interest as a technique for the patterning of functional materials in the liquid phase onto a substrate. Despite its high promise, the phenomena associated with inkjet printing remain incompletely understood. This research project investigates inkjet printing of cellulose nanocrystals (CNCs) as a possible method for the fabrication of cellulose micropatterns. CNCs were prepared from wood pulp by H₂SO₄ hydrolysis and characterized in terms of length, width, and thickness distributions by atomic force microscopy (AFM) and dynamic light scattering. Aqueous CNC suspensions were characterized in terms of shear viscosity with a rheometer. Glass substrates were cleaned with a detergent solution, aqua regia, or a solvent mixture, and characterized in terms of surface chemical composition, surface free energy, polarity, roughness, ζ-potential, and surface charge distribution in air by X-ray photoelectron spectroscopy, contact angle measurements, AFM, streaming potential, and scanning Kelvin probe microscopy (SKPM). Additionally, poly(ethylene glycol)-grafted glass substrates were prepared and characterized in terms of surface free energy, polarity, and roughness. Aqueous CNC suspensions were printed in different patterns onto the different glass substrates with a commercial, piezoelectric drop-on-demand inkjet printer. Inkjet deposited droplet residues and micropatterns were analyzed by AFM, scanning electron microscopy, and polarized-light microscopy. At low CNC concentrations (0.05 wt %), inkjet-deposited droplets formed ring-like residues due to the "coffee drop effect". The "coffee drop effect" could be suppressed by the use of higher CNC concentrations. The resulting dot-like droplet residues exhibited Maltese cross interference patterns between crossed polarizers, indicating a radial orientation of the birefringent, elongated CNCs in these residues. The observed Maltese cross interference patterns represent unprecedented indirect evidence for a center-to-edge radial flow in drying droplets. The degree of definition of the micropatterns depended strongly on the surface properties of the glass substrates. Well-defined micropatterns were obtained on aqua regia-cleaned substrates. In addition to the surface free energy and polarity, other factors seemed to play a role in the formation of the inkjet-printed micropatterns. If these factors can be identified and controlled, inkjet deposition of CNCs could become an attractive method for the fabrication of cellulose micropatterns. / Ph. D.

La complexité des mécanismes de transport en nanofiltration (NF) nécessite ledéveloppement d’outils de modélisation fiables permettant de comprendre et d’optimiser lesopérations de séparation en NF.La présente étude comprend deux volets. Le premier porte sur la rétention d’un soluténeutre – le poly(éthylène glycol) à 600 g mol-1 (PEG) – seul et en présence d’ions, par unemembrane organique de NF (polyamide). Les résultats obtenus montrent que la rétention dusoluté neutre chute en présence d’ions et ce, d’autant plus que la concentration du sel estélevée. Ce phénomène ne peut être expliqué par le seul phénomène de déshydratation dusoluté neutre par les ions environnants. Un phénomène supplémentaire de gonflement de porea été mis en évidence et corrélé à la densité de charge membranaire. La contribution des deuxphénomènes à la chute du taux de rejet du PEG a été évaluée pour différents sels à plusieursconcentrations.Le deuxième volet du travail est consacré à (i) l’évaluation de la constante diélectrique desolutions à l’intérieur de nanopores (ep) d’une membrane organique de NF (polyamide) àpartir de mesures de potentiel de membrane et (ii) la validation de cette méthode. Les valeursobtenues s’avèrent être inférieures à celle de la solution externe (effet du confinement) etdiminuer avec l’augmentation de la proportion en ions calcium du mélange (effet structurantdes ions). L’accord entre les constantes diélectriques ep déterminées à partir de mesures depotentiel de membrane et de taux de rejet ionique (mélanges ternaires) valide la cohérence dumodèle de transport utilisé (exclusion stérique, électrique et diélectrique aux interfaces) etmontre que les mesures de potentiel de membrane peuvent être envisagées pour l’évaluationcorrecte de la constante diélectrique à l’intérieur de nanopores / The complexity of transport mechanisms in nanofiltration (NF) requires the developmentof reliable modelling tools for understanding and optimizing the separation process.This study is composed of two parts. The first one focuses on the retention of a neutralsolute – poly(ethylene glycol) 600 g mol-1 (PEG) – in single solute solutions and in thepresence of mineral salts by an organic NF membrane (polyamide). Results show that PEGrejection is significantly lower in mixed-solute solutions and that rejection rate drop increaseswith salt concentration. This phenomenon cannot be imputed to only the partial dehydrationof PEG molecules by surrounding ions (salting-out effect). The additional hypothesis whichwas considered in the present work is an increase in the effective pore size (pore swelling).This hypothesis was supported by electrokinetics charge density data. The contribution ofpore swelling and salting-out to the overall decrease in the rejection rate of PEG wasevaluated for different salts at various concentrations.The second part of this study deals with (i) the determination of the dielectric constantinside pores (ep) of an NF organic membrane from membrane potential measurements and (ii)the validation of this technique. Membrane potential data were analyzed by means of theSEDE (steric, electric and dielectric exclusion) transport model. ep values were found to besmaller than the bulk value and to decrease when sodium ions were replaced by calcium ions.The agreement between ep values obtained from membrane potential measurements and thosecalculated from ion rejection rate data (ternary mixtures) highlights the global coherence ofthe transport model used and shows that membrane potential measured with electrolytemixtures can be used to determine the dielectric constant inside pores with no requirement ofadditional rejection rate measurements.

This thesis describes the rejection efficiency and the fouling behaviour of calcium sulphate solutes in a 1 nm tubular ceramic titanium dioxide nanofiltration membrane. Calcium sulphate is considered as one of the greatest scaling potential inorganic salts that responsible for membrane fouling which represents a main challenge in the expansion of membrane processes for desalination of brackish and saline water. The surface charge type and magnitude for the composite amphoteric TiO_2 membrane were characterised using streaming potential measurements. Electrokinetic membrane experiments were conducted in a background electrolyte comprising 0.01 M (NaCl). The zeta potential was estimated from the measured streaming potential using the Helmoholtz-Smoluchowski equation and the surface charge density was subsequently calculated using the Gouy-Chapman and Graham equations. The experimental results showed that the membrane was negatively charged at neutral pH and its iso-electrical point (i.e.p) was at pH of 4.0. The rejection behaviour of calcium sulphate at three different initial concentrations (0.001, 0.005 and 0.01 M) were investigated compared to other naturally occurring minerals (NaCl, Na_2 SO_4, CaCl_2) in single salt solutions. The rejection experiments were conducted at five different applied trans-membrane pressures ranged from 1.0 to 5.0 bars. Salt retention measurements showed that the rejection sequence was R (CaSO_4) > R (Na_2 SO_4) > R (CaCl_2) > R (NaCl). This rejection sequence behaviour showed an inverse relationship with the diffusion coefficients of the four salts. The salt with the lowest diffusion coefficient (CaSO_4) showed the highest rejection (43.3%), whereas that with the highest diffusion coefficient showed the lowest rejection. The rejection of calcium sulphate solution at saturation concentration was also conducted after a suspension solution of 0.015 M (CaSO_4) was prepared and filtered. The ionic analysis for calcium sulphate permeates indicated that, for the negatively charged TiO_2 membrane, the rejection for bivalent anion (SO_4^(2-) ) was higher than that of the bivalent cation (Ca^(2+) ).The critical flux (CF) experiments were carried out at six trans-membrane pressure ranged from 1.0 to 6.0 bars to identify the form and the onset of calcium sulphate fouling (as gypsum) using different concentrations below saturation concentration (0.001, 0.005, 0.01 M) and at saturation concentration. Two different flux-pressure techniques have been applied and compared to determine the critical flux values; these are: step by step technique and standard stepping technique. The obtained critical flux results from both measuring techniques (for all the four sessions) confirmed that the critical flux was reached and exceeded. The present work indicated that the resulting critical flux values from both measuring procedures were decreased as the ionic strengths of the calcium sulphate solutes were increased. A mathematical model has been proposed to identify the key parameters that affect the transport performance inside the TiO_2 nanofiltration membrane. The original Donnan steric pore model (DSPM) was used to simulate the rejection of 0.01 M sodium chloride as a reference solution. The membrane effective pore radius was estimated using two different transport models, both of these models depend on the permeation test of uncharged solute (glucose). The Donnan potential was determined based on the membrane effective fixed charge density which was determined by supposing that the membrane surface charge was uniformly distributed in the void volume of cylindrical pores. The theoretical rejection of NaCl solute for the present DSPM model was found to be in agreement with the experimental data.

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