Electrodialysis is a membrane separation process that uses an electrical potential to drive the separation. The performance of these systems is largely based on the performance of their ion exchange membranes (IEMs). This research focused on enhancing the performance of IEMs for electrodialysis through surface modification techniques involving chitosan bonded to the surface of commercially available cation exchange membranes (CEMs). The surface functionalization techniques resulted in membranes with improved electrodialysis performance. This research also explored the processing framework to produce functionalized sulfonated PEEK (sPEEK) nanofibers for future consideration as cation exchange membranes. Chitin was deacetylated to form the functionalized biopolymer chitosan, then applied to the surface of CEMs, rendering them more hydrophilic. These membranes were evaluated across several electrodialysis performance metrics. Results demonstrate that adjusting the degree of deacetylation of chitosan to enhance membrane hydrophilicity positively impacted electrodialysis performance. Furthermore, this research evaluated the effectiveness of similarly functionalized membranes to extract Lithium from brine solutions. The chitosan-coated membranes showed improved electrodialysis performance, including enhanced flux, limiting current density, system resistance, selectivity, and fouling resistance. Lastly, the sPEEK nanofibers were produced for the fabrication of ion exchange membranes by manipulating operational parameters to assess their impact. This research presents the successful functionalization of PEEK via sulfonation and electrospinning of the resulting sPEEK. These nanofibers were then pressed to form a solid sPEEK membrane. It was observed that changes in electrical potential and rotational speed influenced fiber diameter and spinnability. A correlation was established between membrane surface hydrophilicity and electrodialysis performance metrics in desalination and lithium extraction applications. This research advanced the understanding of structure-property relationships for CEMs. The research herein proposes techniques for industries such as desalination and lithium extraction that can meet growing demands for clean water and sustainable methods for producing high-value raw material streams.

Reverse electrodialysis (RED) is a technique that can capture electrical potential from mixing two water streams of different salt concentration through permselective ion exchange membranes. Effective design of ion exchange membranes through structure optimization is critical to increase the feasibility of salinity gradient power production by RED. In this work, we present the preparation of organic-inorganic nanocomposite cation exchange membranes containing sulfonated polymer, poly (2,6-dimethyl-1,4-phenylene oxide), and sulfonated silica (SiO2-SO3H). The effect of silica filler size at various loading concentrations on membrane structures, electrochemical properties, and the RED power performance is investigated. The membranes containing bigger-sized fillers (70 nm) at 0.5 wt% SiO2-SO3H exhibited a relatively favorable electrochemical characteristic for power performance: an area resistance of 0.85 Ω cm2, which is around 9.3% lower than the resistance of the membranes with smaller filler particles. The power performance of this nanocomposite cation exchange membrane in a RED stack showed 10% higher power output compared with the membranes containing small particle size and achieved the highest gross power density of 1.3 W m-2. Thus, further optimized combination of material properties and membrane structure is a viable option for the development of effective ion exchange membrane design, which could provide desirable electrochemical performance and greater power production by RED.

Results have shown that flow batteries may be a solution in the future as an effective and environmental friendly method to an energy storage system (ESS). The technology is reliable and has a high efficiency that comes with low energy losses and a long lifetime. The range of possible fields is suitable for cutting energy peaks in the power grid, by always have a ready and available energy storage that balances the production. By comparing the advantages of flow batteries with conventional batteries it is mainly the fact that they can conserve energy for a long time without being self-discharged thanks to that the storage capacity is in principle endless and limited by the size of the electrolytes tanks that makes them a great energy storage system. The batteries won’t take any damage or decrease in performance when charging or discharging it or if you exhausts it to 100 % and leave it discharged for a long time. The only disadvantages with flow batteries are that they are built upon an advanced design and are built of components made of expensive materials. The main objective of this thesis is to develop an experimental basis for assessing a small pilot module of a flow battery with respect to how different concentrations of salts, flow rates and different currents/voltages affect the performance of the battery. We start by performing the experiment with a polymeric ion exchange membrane and see what values and the advantages and disadvantages it entails.

Le colmatage à la surface et dans la masse d’une membrane échangeuse d’ions est un obstacle majeur à son utilisation en électrodialyse. En bloquant les voies conductrices d’ions à travers la membrane, le dépôt réduit la surface active de la membrane et conduit à une résistance au transfert de matière supplémentaire.Trois membranes échangeuses de cations ont été utilisées lors de ce travail: une membrane commerciale hétérogène MK-40 et deux de ses modifications (une membrane MK-40/Nafion obtenue par revêtement de la surface de MK-40 avec un film de Nafion® homogène conducteur d’ions, et une membrane MK-40/PANI obtenue par synthèse de polyaniline sur la surface de la MK-40). Les solutions utilisées sont des solutions de CaCl2 et MgCl2 aux concentrations 0,02 et 0,04 mol/L, ainsi qu’une solution modélisant la composition minérale du lait, concentrée 3 fois. La visualisation de la surface de la membrane est réalisée par microscopie optique et microscopie électronique à balayage. L’analyse élémentaire des dépôts sur la surface de la membrane est réalisée par l’analyse aux rayons X. Le caractère hydrophobe-hydrophile de la surface de la membrane est estimé par la mesure de l’angle de contact. La chronopotentiométrie et la voltamétrie ont été utilisées pour caractériser la vitesse de transport des cations à travers les membranes et la dissociation d’eau à la surface ; la mesure du pH de la solution dessalée a été effectuée en parallèle.Il est démontré que l’hydrophobicité relativement élevée de la surface de la membrane, son hétérogénéité électrique et géométrique créent les conditions favorables au développement de l’électroconvection. L’intensité de l’électroconvection par rapport à la membrane non modifiée est significativement plus élevée dans le cas de la MK-40/Nafion mais plus faible dans le cas de la MK-40/PANI. L’électroconvection provoque le mélange de la solution à la surface de la membrane dans une couche d’environ 10 µm d’épaisseur. Cet effet augmente de manière significative le transfert de matière en mode de courant intensif, empêche ou réduit le colmatage et réduit aussi le taux de dissociation de l’eau sur la surface de la membrane. L’intensité de l’électroconvection dépend essentiellement du degré d’hydratation du contre-ion ; elle augmente avec son rayon de Stokes. Le taux de croissance des dépôts minéraux Mg(OH)2, Ca(OH)2 et CaCO3 sur la surface de la membrane échangeuse d’ions est déterminé par la pente du chronopotentiogramme. On établit expérimentalement que, par rapport à la vitesse de colmatage sur la membrane MK-40 non modifiée, celle sur la surface de MK-40/Nafion devient plus petite mais celle sur la surface de la MK-40/PANI, devient plus grande.Le taux du colmatage est considérablement réduit lorsqu’un mode de courant électrique pulsé est appliqué. Un tel mode permet de réduire de moitié la différence de potentiel et d’atteindre un état quasi-stable du fait que le précipité devient instable / Scaling on the surface and in the bulk of ion-exchange membranes is a considerable locker for electrodialysis. The scale reduces the effective surface area of the membrane and leads to additional resistance to the mass transfer and solution flow.Three cation-exchange membranes are used in this study: a heterogeneous commercial MK-40 membrane and two of its modifications. The MK-40/Nafion membrane is obtained by mechanical coating the MK-40 membrane surface with a homogeneous ion-conductive Nafion® film. Modification of the MK-40/PANI membrane is carried out by polyaniline synthesis on the membrane surface. The solutions used in the study are 0.02 and 0.04 mol/L CaCl2 and MgCl2 solutions, as well as the solution, imitating the mineral composition of milk, concentrated 3 times. The visualization of the membrane surface is made using optical and scanning electron microscopy. The elemental analysis of the scale on the membrane surface is made by X-ray analysis. The hydrophobic-hydrophilic balance of the membrane surface is estimated by the contact angle measurements. To characterize the cation transport through and the water splitting rate, chronopotentiometry and voltammetry methods are used, pH measurement of the diluate solution is conducted at the same time.It is shown that the relatively high hydrophobicity of the membrane surface, its electrical and geometric heterogeneity, create conditions for the development of electroconvection. The electroconvection intensity in the case of MK-40/Nafion is significantly higher, and in the case of MK-40/PANI is lower in comparison with that of the unmodified membrane. Electroconvection vortexes cause the mixing of the solution at the membrane surface in a 10 µm thick layer. This effect significantly increases mass transfer in intensive current modes and prevents or reduces the scaling process, as well as reduces the water splitting rate at the membrane surface. The rate of electroconvection essentially depends on the counterion hydration degree, it increases with increasing the counterion Stokes radius. The rate of the scale formation on the membrane surface is determined by the slope of the chronopotentiogramme. The formation of Mg(OH)2, Ca(OH)2 and CaCO3 scales is observed. It is experimentally established that the scaling rate on the surface of MK-40/Nafion is smaller, and on the surface of the MK-40/PANI is larger in comparison with the MK-40 membrane. The scaling rate is significantly reduced when the pulsed electric current mode is applied. Such mode allows the reduction of the potential drop more than twice and achievement of a quasi steady-state because an unstable periodically crumbling scale occurs

Nitrogen deficiency is characteristic of many mid-rotation loblolly pine (Pinus taeda L.) plantations in the Piedmont region of the southeastern USA. Fertilization with urea is the most common method used to correct this deficiency. Previous studies show that urea fertilization produces a rapid pulse of available nitrogen (N) with only a portion being utilized by plantation trees. Controlled release fertilizers release available N more slowly over a longer period of time and therefore may result in greater uptake efficiency. The objective of this study was to compare Nitroform®, a urea-formaldehyde controlled release N fertilizer versus urea and a control by measuring the effects of the two fertilizer treatments on N availability and loss as: total KCl extractable-N, total ion exchange membrane-N (IEM-N), N mineralization, and N volatilization, in a mid-rotation loblolly pine plantation in the Piedmont of Virginia. In addition, mid-summer and mid-winter fertilizations were compared to assess fertilizer uptake as a function of season. After the summer fertilization, Nitroform® significantly increased total KCl-extractable N, IEM-N, and N mineralization for two to three months over urea and the control. Three hundred times more N volatilized from urea than from controlled release Nitroform®. Interestingly, seven months after the summer application, the controlled release Nitroform® showed marked immobilization for three months while urea demonstrated greater N mineralization. After the winter application, fertilization with urea demonstrated greater soil inorganic N concentrations for two to three months over Nitroform®, very little N was immobilized, and volatilization was only 10 times that of Nitroform®. After summer and winter fertilizations, both fertilizer treatments significantly increased soil inorganic N concentrations and N volatilization over controls, however did not significantly increase N mineralization over controls when average response was tested over the entire sampling period. In addition to the fertilizer effects measured, a thinning only treatment was also incorporated into this study with soil N-availability indices compared to a control with no thinning or fertilization. The results from the thinning only treatment demonstrated no significant increases over the control in total KCl extractable-N, IEM-N, N-mineralization, or N volatilization when average responses were tested over the entire sampling period. / Master of Science

L'électrodialyse peut être utilisée pour traiter des effluents salins contenant de la matière organique. La compréhension des mécanismes de transfert (eau, ions, espèces organiques) à travers les membranes échangeuses d'ions et particulièrement l'influence de la composition ionique est un point clé vis-à-vis des performances du procédé. L'objectif de cette thèse est l'étude du transfert et la relation avec les performances de dessalement. Les nombres d'hydratation des ions sont tout d'abord calculés à partir des mesures du transfert des ions et de l'eau. Ils sont indépendants du courant et de la composition saline. La comparaison avec des valeurs de la littérature montre que les membranes ont peu d'effet sur l'hydratation des ions. Le transfert d'espèces organiques est ensuite étudié pour différentes compositions salines. Outre la diffusion, une contribution additionnelle est mise en évidence (convection pour les espèces neutres, migration pour les espèces chargées). Pour les espèces neutres, diffusion et convection sont du même ordre de grandeur et fixées par l'effet stérique. Des tendances inverses sont obtenues concernant l'hydratation des ions, la diffusion étant limitée par les modifications des membranes, la convection étant limitée par l'hydratation des espèces organiques en solution. Pour les espèces chargées, la migration domine la diffusion, les deux contributions étant influencées par la présence de sel. Les performances de dessalement sont enfin discutées sur la base d'un modèle phénoménologique à 4 paramètres liés au transfert de l'eau, des ions et des espèces organiques. La robustesse du modèle est validée pour différentes conditions. Ce travail montre que l'électrodialyse est une technologie très prometteuse pour le dessalement d'effluents contenant de la matière organique. / Electrodialysis can be used to treat saline water containing organic solute, separating organic solutes from salt. The understanding of salt, water and organic solute transfer through ion- exchange membranes and especially the influence of salt composition is a key factor regarding the process performances. The aim of the Thesis is to investigate the mass transfer and the relationship with the desalination performance. Firstly, hydration numbers of individual ion transferring through the membranes are computed based on experimental measurements of ion- water flux. They are independent from the salt compositions and current. Comparison with literatures values shows that the membranes have a weak influence on the ion hydration. Secondly, the transfer of different organic solutes is investigated with different salt compositions. Two contributions are pointed out, diffusion and additional one (convection for neutral solute, migration for charged one). For neutral solutes, diffusion and convection are comparable and both fixed by steric effect. Ion hydration leads to reversed trend for diffusion due to membrane swelling and convection due to solute dehydration. For charged solute, migration is more important than diffusion, both being influenced by the presence of salt. Then, desalination performance is discussed based on a phenomenological model, consisting of 4 parameters, related to ion, water and organic solute transfer respectively. The robustness of the model is demonstrated for different conditions. This work shows that electrodialysis can be a very promising process for the desalination of saline water containing organic solutes.

Increased levels of nitrate in ground water have made many wells unsuitable as sources for drinking water. In this thesis an ion-exchang eassisted electromembrane process, suitable for nitrate removal, is investigated both theoretically and experimentally. An ion-exchange textile material is introduced as a conducting spacer in the feed compartment of an electropermutation cell. The sheet shaped structure of the textile makes it easy to incorporate into the cell. High permeability and fast ion-exchange kinetics, compared to ion-exchange resins, are other attractive features of the ion-exchange textile. A steady-state model based on the conservation of the ionic species is developed. The governing equations on the microscopic level are volume averaged to give macro-homogeneous equations. The model equations are analyzed and relevant simplifications are motivated and introduced. Dimensionless parameters governing the continuous electropermutation process are identified and their influence on the process are discussed. The mathematical model can be used as a tool when optimising the process parameters and designing equipment. An experimental study that aimed to show the positive influence of using the ion-exchange textile in the feed compartment of an continuous electropermutation process is presented. The incorporation of the ion-exchange textile significantly improves the nitrate removal rate at the same time as the power consumption is decreased. A superficial solution of sodium nitrate with a initial nitrate concentration of 105 ppm was treated. A product stream with less than 20 ppm nitrate could be obtained, in a single pass mode of operation. Its concluded from these experiments that continuous electropermutation using ion-exchange textile provides an interesting alternative for nitrate removal, in drinking water production. The predictions of the mathematical model are compared with experimental results and a good agreement is obtained. Enhanced water dissociation is known to take place at the surface of ion-exchange membranes in electromembrane processes operated above the limiting current density. A model for this enhanced water dissociation in presented in the thesis. The model makes it possible to incorporate the effect of water dissociation as a heterogeneous surface reaction. Results from simulations of electropermutation with and without ion-exchange textile incorporated are presented. The influence of the water dissociation is investigated with the developed model. / QC 20101118

El objetivo principal de este trabajo es desarrollar un modelo sencillo que permita la caracterización hidrodinámica de membranas selectivas integradas en sistemas bi-iónicos, mediante la determinación de coeficientes de difusión y de espesores de las capas límite alrededor de la membrana. A tal fin, se empleó una célula de difusión rotatoria (CDR), que permite el establecimiento de condiciones hidrodinámicas bien definidas para el sistema de membrana, dado que la variación de la frecuencia de giro del cilindro interior (ω), permite disminuir el espesor de la capa límite sobre la membrana, lo que favorece el intercambio iónico a su través. Se puede comprobar éste comportamiento, mediante consideraciones en torno al coeficiente de difusión de los cationes en el sistema de membrana y del cálculo del propio espesor de la capa límite. El mencionado coeficiente se obtendrá a partir del flujo iónico en la membrana, determinado a partir de medidas de pH, junto a medidas de conductividad, en la fase externa (receptora), a diferentes temperaturas y a distintas valores de ω.La medida de los flujos, una vez establecida su dependencia con ω, permite obtener los coeficientes de difusión catiónicos en el sistema de membrana, en función de la temperatura y de ω. Las medidas de la conductividad permiten testar el modelo propuesto, mediante su correlación con los valores de pH obtenidos, proporcionando información adicional acerca de los coeficientes de difusión de los cationes. / From the experimental study of the ionic transport through selective membranes in biionic systems, a simple model which allows the characterising hydrodynamic of the membrane systems through the determination of diffusion coefficients and the thickness of the limit layer has been developed. With this purpose, a rotating diffusion cell that allows the setting of hydrodynamic conditions clearly for the membrane system has been used, studying the variation of the conductivity and the pH in the external phase (receiving) at different temperatures from 20ºC to 50ºC and at different rotating velocities ω. The measurement of the fluxes, once set its dependence with ω, allows obtained the diffusion coefficients cationics in the membrane system in accordance with the temperature and ω. The measurements of the conductivity allow the testing of this model, through its correlation with the values of the pH measured, obtaining additional data about the diffusion coefficient of the cations in the receiving phase.

<p>Increased levels of nitrate in ground water have made many wells unsuitable as sources for drinking water. In this thesis an ion-exchang eassisted electromembrane process, suitable for nitrate removal, is investigated both theoretically and experimentally. An ion-exchange textile material is introduced as a conducting spacer in the feed compartment of an electropermutation cell. The sheet shaped structure of the textile makes it easy to incorporate into the cell. High permeability and fast ion-exchange kinetics, compared to ion-exchange resins, are other attractive features of the ion-exchange textile.</p><p>A steady-state model based on the conservation of the ionic species is developed. The governing equations on the microscopic level are volume averaged to give macro-homogeneous equations. The model equations are analyzed and relevant simplifications are motivated and introduced. Dimensionless parameters governing the continuous electropermutation process are identified and their influence on the process are discussed. The mathematical model can be used as a tool when optimising the process parameters and designing equipment.</p><p>An experimental study that aimed to show the positive influence of using the ion-exchange textile in the feed compartment of an continuous electropermutation process is presented. The incorporation of the ion-exchange textile significantly improves the nitrate removal rate at the same time as the power consumption is decreased. A superficial solution of sodium nitrate with a initial nitrate concentration of 105 ppm was treated. A product stream with less than 20 ppm nitrate could be obtained, in a single pass mode of operation. Its concluded from these experiments that continuous electropermutation using ion-exchange textile provides an interesting alternative for nitrate removal, in drinking water production. The predictions of the mathematical model are compared with experimental results and a good agreement is obtained.</p><p>Enhanced water dissociation is known to take place at the surface of ion-exchange membranes in electromembrane processes operated above the limiting current density. A model for this enhanced water dissociation in presented in the thesis. The model makes it possible to incorporate the effect of water dissociation as a heterogeneous surface reaction. Results from simulations of electropermutation with and without ion-exchange textile incorporated are presented. The influence of the water dissociation is investigated with the developed model.</p>

The biological translation between biological and electrical signals have inspired scientists over the last decade and has opened new way of therapeutics. The group of Bioelectronics at the Laboratory of organic electronics (LOE) develops systems that utilizes this translation to reduce the gap between electronics and biology. A known example of devices that does this are called iontronic delivery devices. These devices allow very specific transport and delivery of charged compounds. The most basic iontronic delivery device is the organic electronic ion pump (OEIP). The OEIP have been developed and fabricated into many variations, for example the iontronic micropipette which is a device that has been developed at LOE. In this project, the fabrication and characterization of the iontronic micropipette have been developed to find fabrication parameters that generates stable, high performing and reproduceable devices together with good and reproduceable characterization protocols. The iontronic micropipette is fabricated in a cleanroom and characterized in two steps, optically in a microscope and then electrically by transporting ions through the membrane. Two different membrane materials were tested, 2- acrylamido-2-methylpropane sulfonic acid (AMPSA) and Hyperbranched polyglycerols (HPG). The results that were obtained from the fabrication of the AMPSA showed a reproducibility between many devices, but many AMPSA device broke during the fabrication so the protocol for the AMPSA still need improvement. Regarding the A-HPG fabrication, the results were much more positive and the yield from the fabrication were sufficient. The results that were obtained in the characterization of the AMPSA device showed that these devices had a very equal resistance between the device from the same batch. For the A-HPG, it was a much larger spread in the resistance between the device but the resistance were still much lower than for the AMPSA which is more preferable for most applications on living cells. / <p>Examensarbetet är utfört vid Institutionen för teknik och naturvetenskap (ITN) vid Tekniska fakulteten, Linköpings universitet</p>