Selective ion separations are gaining increasing importance across water, energy, and environmental sectors. Ion-exchange membranes (IEMs), which are charged polymeric films, have been playing a crucial role in diverse applications, such as electrodialysis (ED) desalination, redox flow batteries, and chloralkaline processes. However, the growing demand for enhanced selectivity poses challenges to current IEMs, necessitating improved membrane separation capabilities beyond simple charge selection between cations and anions. The objective of this thesis is to advance the selectivity of IEMs, moving them closer to becoming ion-selective membranes. Specifically, the research deepens the fundamental understanding of transport phenomena in IEMs and develops novel membranes with improved specific ion selectivity, permselectivity, and ion/water selectivity. In IEM processes, the correlation between conductivity and permselectivity, representing the selectivity of counterion oppositely charged to the membrane against like-charged co-ion, significantly impacts process performance. The dissertation work first investigates the tradeoff between conductivity and permselectivity of IEMs, arising from variations in solution concentrations (Chapter 2). These tradeoff patterns are broadly observed across diverse electrolytes, which are primarily influenced by factors including valencies of counter- and co-ions, as well as counterion diffusion coefficients. The research next delves deeper into the mobility of condensed counterions in IEMs (Chapter 3). An analytical model is introduced to depict the mobility of condensed counterions, facilitated by the novel utilization of a scaling relationship to accommodate the screening length in highly charged IEM matrices. Upon integrating the contributions of condensed counterions, the Donnan-Manning transport framework accurately predicts IEM conductivities in monovalent counterions, aligning closely with experimental values (as small as within 7%) and devoid of adjustable parameters. The analysis underscores the greater mobility of condensed counterions compared to their uncondensed counterparts, as electrostatic interactions accelerate condensed counterions while impeding uncondensed counterions. The advancements in transport theories concerning conventional IEMs, as presented in Chapters 2 and 3, provide vital insights into the selectivity limitations of existing membranes, emphasizing the necessity for IEMs with improved selectivity. The thesis then transitions to the development of IEMs tailored for specific ion selectivity. This endeavor involves engineering water-deficient sulfonated polystyrene membranes to leverage discrepancies in ion hydration free energy, thereby refining selectivity between counterions with identical valence (Chapter 4). The fabricated membranes prefer the transport of K+ over Li+ in ED, with the K/Li transport selectivity increasing from 2.5 to 3.1 as the membrane's water deficiency, represented by the number of water molecules per fixed charge site (λ), declined from 12 to 6.3. Further analysis of ion sorption behaviors highlights selective partitioning as the primary driving factor, with K+ showing a greater affinity into the membrane at lower λ levels as a result of its lower hydration free energy. In addition to polymeric membranes, the work also explores composite ceramic IEMs employing sol-gel chemistry to achieve tunable selectivity among different counterions (Chapter 5). Significantly, the resulting membranes display an impressive K/Li transport selectivity of up to 6.3 in the ED measurements, surpassing many research efforts focused on polymeric materials. This remarkable selectivity primarily stems from the preferential sorption of K+ into the ceramic matrix. Moreover, these membranes demonstrate excellent differentiation between monovalent and divalent counterions, with Li/Mg and Na/Ca transport selectivity values of 17 and 29, respectively, obtained in the ED process, rivaling or even leading commercial products. ED shows great potential for cost-effective hypersaline desalination; however, its effectiveness has been limited by the absence of suitable IEMs with high permselectivity and ion/water selectivity in high-salinity conditions. This work presents the development of highly charged and low-swelling IEMs customized for high-salinity ED desalination, achieved through a facile sulfonation strategy of polystyrene (Chapter 6). The heightened fixed charge density enables fabricated membranes to sustain remarkable permselectivity, exceeding 0.96 in ED characterization with 4 M NaCl solution, which far transcends that of commercial IEMs. Furthermore, these membranes effectively suppress osmotic water permeability and electro-osmosis at lower water content. The performance of hypersaline ED desalination is improved by employing the developed membrane to treat synthetic brine, together with the successful desalination of practical feed. This dissertation significantly enhances our comprehension of membrane transport phenomena and showcases the strategic development of innovative IEMs with advanced selectivity. The progression in transport theories offers crucial insights into the structure-property-performance relationships of IEMs, while highlighting the selectivity constraints of current membranes. The work demonstrates straightforward strategies for producing membranes capable of distinguishing between different counterions, including water-deficient polymeric membranes and composite ceramic membranes. The highly charged and low water content membranes customized to achieve improved permselectivity and ion/water selectivity enable efficient electromembrane processes under high-salinity conditions. The findings of the thesis contribute to the eventual realization and deployment of ion-selective membranes to address water, energy, and environmental concerns.

Winter wheat is commonly grown in rotation with leguminous and non-leguminous crops in the Willamette Valley. For agronomic, economic, and environmental reasons it is important to understand the influence of previous crops on availability of N and other nutrients. Objectives of this study were: (1) to evaluate the effects of long-term rotations on winter wheat response to N fertilizer, and (2) to evaluate the use of Plant Root Simulator���(PRS) probes for measuring soil N mineralization and N availability to winter wheat. Field experiments were conducted over three growing seasons in plots of `Stephens' soft white winter wheat at Hyslop farm. Plots receiving 0, 50, 100, 150 and 200 kg N ha����� at Feekes GS 4 were sampled to determine above ground N uptake, grain yield, and grain protein. In spring 1998, PRS probes were placed in 0 kg N ha����� plots and removed at one-week or two-week intervals. In autumn 1998, probes were placed in unfertilized plots and removed at 1-week, 4-week, and 8-week intervals. Probes measured the availability of NH������-N, NO������-N, K���, Ca�����, Mg�����, and P0��������-P. Grain yield and N uptake were greater for wheat following clover as compared to following oats. Three-year average fertilizer equivalent values calculated from N uptake and grain yield data were 44.5 kg N h����� and 49.0 kg N h�����, respectively. The similarity of these independent measurements suggest that differences in N availability were the primary reason for the rotation effect. PRS probes also detected rotational differences in N availability. Average N recovered by probes sampled at 1-week intervals indicated that there was 63% as much NO������-N available to wheat following oat as compared to clover. Wheat recovered 64% as much N following oats as compared to clover. This suggests that PRS probes are an effective method for predicting relative amounts of plant available N. PRS probes also detected rotational differences in plant available potassium. Agronomic responses are useful for assessing the availability of nutrients that are limiting plant growth. PRS probes, on the other hand, are effective for assessing the availability of both limiting and non-limiting nutrients. / Graduation date: 2000

My main objective is to gain a firm understanding of the correlation between the defect chemistry and the properties of Ba-based perovskite structure proton-conducting ceramics, especially B-site doped BaCeO3, so as to allow the engineering of these compounds with the desired properties for the application in devices; develop membranes of mixed protonic-electronic conductors suitable for hydrogen separation from gas mixtures; and further advance hydrogen separation technology by gaining fundamental understanding about electrochemical separation mechanism. BZCY proton conductors with various compositions have been synthesized and characterized. The absence of low-angle supercell reflections indicates a random B-site cation distribution. The substitution of Zr led to a decrease in cell volume and an enhanced structural stability against reactions with CO2. The total conductivity for BZCY pellets increased with temperature increased and decreased as the zirconium content increased at each fixed temperature. Dense Ni-BZCY composite membranes have been successfully fabricated for evaluating hydrogen permeability and stability. Doping Zirconium in the B-site only slightly reduced the hydrogen permeation at high temperatures, but dramatically increased the chemical stability in CO2- and H2O-containing gases. Among the compositions studied, the Ni-BZCY7 exhibited both highest H2 permeation rate and good chemistry stability, thus having potential for practical applications.

Soil phosphate is essential for the development and maturity of crops. Plants absorb phosphate from the soil solution which is continuously replenished by fertilizer application and/or desorption from the soil solid phase. Anion exchange membranes (AEMs), act in a similar way to plant roots, adsorbing P from soil solution. Desorption of available P was studied in 1997 on two Gleysolic soils rich in P, a Ste. Rosalie clay soil and a Duravin sandy loam soil, using fluoride-saturated AEMs let in soil suspension for various contact periods. Determination of available P using these AEMs was compared to P extraction using the Mehlich III extractant for predicting P availability to soybean (Glycine max L.). Desorption from both soils, and subsequent adsorption by AEMs was found to decrease with time. A high P desorption rate was calculated for both soils with the Elovich equation. Different chemical and physical characteristics such as pH, Mehlich III extractable Al, Fe and Ca, sand and clay content were in some cases, positively correlated and in other cases, negatively correlated with various contact periods for both soils. The use of AEMs better predicted P availability than the Mehlich III extractant, although the most important asset of using AEMs is that they showed the desorption effect over time on P availability. It was observed that P remobilization from the vegetative part to the grain was reduced due to the high P concentration in both soils.

Bibliography : leaves 197-209 / 210 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Botany, 1991

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<p align="justify">Des membranes échangeuses anioniques à base de polysulfone, portant des sites échangeurs de type ammonium quaternaire, ont été préparées. Misant sur la possibilité d’établissement d’interactions spécifiques entre les espèces échangées et les sites chargés, nous avons fait varier la longueur des chaînes alkyles sur l’azote de un à trois carbones, dans le but de moduler le transport d’anions caractérisés par des propriétés d’hydratation différentes.</p><p><p><p align="justify">La réaction d’halométhylation a été choisie pour l’introduction préalable sur le squelette polymérique de groupements précurseurs des sites ioniques. Une étude cinétique de la réaction a permis d’établir des conditions compatibles avec un haut taux de substitution et une absence de réticulation. Des réactions d’amination ont été sélectionnées pour la conversion des sites précurseurs en sites ammoniums quaternaires. L’étape d’élaboration du film s’est avérée essentielle pour l’obtention de membranes et peut être réalisée avant et après l’amination. Nous avons mis en évidence que l’encombrement stérique du réactif entrave la diffusion de celui-ci au sein d’un réseau polymérique dense et peut entraîner une déstructuration mécanique des films. Par conséquent, pour l’introduction de sites ammoniums quaternaires à chaînes alkyles de plus d’un carbone, des réactions en solution se sont révélées plus appropriées.</p><p><p align="justify">L’hydratation d’une membrane comportant des sites ammoniums quaternaires à chaînes latérales méthylées a été étudiée par spectroscopie vibrationnelle. Des modifications induites par l’hydratation apparaissent sur les spectres IR et Raman du polymère. L’interprétation de ces changements nous a amenés à conclure que les groupements éther et sulfone, tous deux électronégatifs, interagissent avec les sites ammoniums quaternaires dans la membrane sèche. L’entrée d’eau dans la membrane empêche l’existence de ces interactions en éloignant les chaînes polymériques les unes des autres.</p><p><p align="justify">L’ensemble des membranes préparées dans le cadre de ce travail a été caractérisé du point de vue des propriétés électromembranaires de résistance électrique, de densité de courant limite et de sélectivité nitrate versus chlorure. Nous avons mis en évidence qu’un allongement des chaînes alkyles sur l’azote de un à trois carbones conduit à une sélectivité accrue pour le nitrate, anion caractérisé par une enthalpie libre d’hydratation moins négative que le chlorure. Avec des chaînes alkyles de trois carbones sur l’azote, la membrane laisse passer jusqu’à treize anions nitrate pour un anion chlorure. Ces résultats indiquent que la sélectivité des membranes synthétisées peut effectivement être contrôlée par les interactions spécifiques s’établissant entre l’ion échangé et le site échangeur. Nous avons aussi montré que la résistance des membranes diminue jusqu’à environ 1 <font face="Symbol, serif">W</font> cm2 suite à leur réimmersion dans un bain d’amine. L’influence de cette étape de réimmersion est discutée.</p> / Doctorat en sciences, Spécialisation chimie / info:eu-repo/semantics/nonPublished

Indiana University-Purdue University Indianapolis (IUPUI) / The innovation and investigation of catalysts in proton exchange membrane fuel cells are included in this thesis. In the first part of this work, stability of the catalyst support of PEMFC catalyst is investigated. Nanoscale platinum particles were loaded on two different kinds of carbon supports, nano graphene sheets and functionalized carbon black/graphene hybrid were developed by the liquid phase reaction. The crystal structure of two kinds of catalysts was characterized by X-ray diffractometer (XRD). The morphology and particle size were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). Pt loading was measured by thermal gravimetric analysis (TGA). The Brunauer, Emmett and Teller (BET) method was applied to test the surface area of the catalysts. The electrochemical surface area (ECSA) and mass activity during oxygen reduction reaction (ORR) process for two kinds of catalyst were tested by cyclic voltammetry method under different conditions. The stability of the catalysts were tested by accelerated durability test (ADT). The results show that although the mass activity of Pt/graphene is much lower, the stability of it is much better than that of the commercial catalyst. After adding functionalized carbon black (FCB) as spacer, the stability of the catalyst is preserved and at the meantime, the mass activity becomes higher than 20% Pt/XC72 catalyst. The lower mass activity of both catalysts are due to the limitation of the electrolyte diffusion into the carbon support because of the aggregation nature of graphene nano-sheets. After introducing functional carbon black as spacer, the mass activity and ECSA increased dramatically which proved that FCB can be applied to prevent the restacking of graphene and hence solved the diffusion problem. In the meantime, the durability was still keeping the same as Pt/graphene catalyst. In the second part of the work, the restacking problem was solved by introducing FCB as spacers between functionalized graphene nanosheets. The same measurement was applied to test the electrochemical performance of Pt/FCB/FG catalyst. The new catalyst showed a higher mass activity compared to Pt/graphene catalyst which meant the restacking problem was partially solved. The durability of the Pt/FCB/FG catalyst was still excellent.

Ce travail porte sur l'amélioration de la sélectivité préférentielle d'une membrane cationique à base d’ETFE pour une utilisation en électrodialyse afin de traiter des effluents industriels contenant un mélange d’acides et de sels métalliques. Pour cela, nous avons fait appel à la méthode de la modification chimique de la surface d’une membrane cationique par la formation d’un film superficiel mince portant des charges positives afin de former une barrière de répulsion électrostatique pour des cations bivalents tout en permettant le passage de cations monovalents tels que les protons.<p>La synthèse de la membrane cationique de base a été réalisée en passant par différentes étapes à savoir :le greffage du styrène - divinylbenzène (DVB), la chlorosulfonation et l’hydrolyse. <p>Au cours de ce travail, nous avons mis au point un protocole de greffage du styrène-DVB dans le film d’ETFE qui permet l’obtention d’un film ayant un taux de greffage reproductible assurant à la membrane cationique finale une bonne conductivité électrique et une capacité d’échange acceptable pour une membrane d’électrodialyse. Une étude de la réaction de greffage en fonction de la concentration en réticulant a été réalisée. <p>Nous avons procédé par la suite à la modification de la surface du film d’ETFE greffé styrène-DVB par la formation d’une couche superficielle mince fixée par des liens covalents. Les membranes modifiées ont été obtenues par la réaction d’une seule face du film d’ETFE greffé chlorosulfoné avec la 3-diméthylaminopropylamine. La modification chimique de la surface du film ETFE greffé chlorosulfoné a été suivie par la technique FTIR-ATR. L’effet de la concentration de la diamine sur les propriétés électrochimiques des différentes membranes modifiées a été étudié. La résistance électrique des membranes modifiées équilibrées au contact de solutions de chlorure de sodium et d'acide sulfurique a été mesurée par la technique d’impédance. La détermination du nombre de transport du proton et de l’ion sodium a été réalisée à partir de mesures du potentiel de membrane. La densité de courant limite des membranes a été évaluée sur base des courbes courant-tension. Les mesures de chronopotentiométrie ont été également effectuées sur les différentes membranes synthétisées.<p>Les résultats de ces caractérisations montrent que la modification de la surface engendre des changements considérables au niveau des propriétés électrochimiques des membranes résultantes. La résistance électrique, la densité de courant limite ainsi que les propriétés de transport de la membrane dépendent d’une part de la concentration de la diamine utilisée et d’autre part de la solution dans laquelle la membrane modifiée est équilibrée. <p>La sélectivité préférentielle des différentes membranes vis-à-vis des protons par rapport aux ions bivalents a été testée en réalisant des électrodialyses d’un milieu mixte H2SO4-NiSO4. Nos résultats montrent que la modification chimique de la surface de la membrane affecte d’une manière significative le transport des ions nickel tout en respectant le passage des protons. Une meilleure séparation a été obtenue pour une membrane modifiée en utilisant la diamine pure.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished