No description available.

As the demand on resources is increasing worldwide, the process of recycling material has become more important. The specific recycling of metals used in car batteries, and more specifically in the large batteries used in hybrid electric vehicles, is a rising concern where the industrially implemented recycling processes concerning these batteries that exist today are often highly pollutant and energy consuming. In the present study, an alternative hydrometallurgical recycling process of the previously and to some extent presently widely used battery type for hybrid electric vehicle applications, namely the Nickel Metal Hydride (NiMH) battery, has been investigated. The focus was to evaluate different routes of recovering Ni, Co, Mn, Zn, Al and residual Y from a NiMH battery leach solution as obtained in a priorly conducted leaching study. Three different possible products were chosen for closer investigation, a mixed metal hydroxide where all of the metals would be precipitated together, a new NiMH cathode material where a controlled precipitation of Ni, Co and Zn together would be implemented and last a pure Ni salt product where a selective separation of Ni from the other metals would be required. Two of the three products, the mixed metal hydroxide and the pure Ni salt, were found suitable for the specific system and it was concluded that a pure Ni salt production would be most justifiable. The separation of Ni from the other metals present in the solution was here proposedly achieved by an extraction process using supported liquid membranes. A mathematical model was used in Matlab in order to evaluate the separation efficiency and to determine the optimum process conditions for the extraction process and a hydroxide precipitation experimental study was conducted in order to determine both the process streams in the production of a mixed metal hydroxide and the solution behavior during the pH increase in the Ni salt production extraction process. The results suggested a low loss of valuable metals and due to this, both the process of producing a mixed metal hydroxide and the process of producing a pure Ni salt could be found to be economically justifiable. / I samband med den ökande efterfrågan på råmaterial världen över så har processer för att återvinna material blivit mer och mer viktiga. Den specifika återvinningen av metaller som använts i bilbatterier, och än mer specifikt återvinningen av de stora batterier som används i hybridbilar är just nu en ökande oro då de rådande återvinningsprocesser som används idag ofta är högst energikrävande och har en stor förorenande inverkan på naturen. I denna studie har en alternativ hydrometallurgisk återvinningsprocess granskats i syfte att återvinna de metaller som används i nickelmetallhydridbatterier (NiMH) som brett har använts för just hybridbilsapplikationer. Fokus har legat på att utvärdera olika möjligheter att återvinna Ni, Co, Mn, Zn, Al och överbliven Y från en laklösning som är ett resultat av en tidigare genomförd lakstudie angående NiMH-batterierna. Tre möjliga produkter valdes för närmare granskning, en blandad metallhydroxid där alla metaller samutfälls ur lösningen, en ny NiMH-katod där en kontrollerad samutfällning av Ni, Co och Zn implementeras och sist ett rent nickelsalt där a selektiv separation av Ni från de övriga metallerna är nödvändig. Två av de tre produkterna, den blandade metallhydroxiden och det rena nickelsaltet, befanns vara lämpliga för det specifika systemet och slutsatsen drogs att en nickelsaltsproduktion var mest berättigad. Den föreslagna separationstekniken för att separera Ni från de andra metallerna i lösningen var en extraktionsprocess användandes av en vätskemembranteknik. En matematisk modell användes med hjälp av Matlab för att utvärdera separationseffektiviteten och för att bestämma optimala processförhållanden. En experimentell hydroxidutfällningsstudie genomfördes även för att bestämma både procesströmmarna i en produktion av en blandad metallhydroxid och för att undersöka lösningens beteende under pH-ökningen i den föreslagna produktionsprocessen av ett nickelsalt. Enligt resultaten är förlusten av värdefulla metaller låga i båda processerna och i enlighet med detta kunde både produktionsprocessen av en blandad metallhydroxid och av ett rent nickelsalt befinnas ekonomiskt hållbara.

No description available.

Bioanalytical chemistry is a challenging field, often involving complex samples, such as blood, plasma, serum or urine. In many applications, sample cleanup is the most demanding and time-consuming step. In the work underlying this thesis a novel dynamic miniature extractor, known as a hollow-fibre liquid-phase microextractor (HF-LPME), was designed, evaluated and studied closely when used to clean plasma samples. Aqueous-organic-aqueous liquid extraction, in which the organic liquid is immobilised in a porous polypropylene membrane, was the principle upon which the extractor was based, and this is discussed in all the papers associated with this thesis. This type of extraction is known as supported-liquid membrane extraction (SLM). The aim of this work was the development of a dynamic system for SLM. It was essential that the system could handle small sample volumes and had the potential for hyphenations and on-line connections to, for instance, LC/electrospray-MS. The design of a miniaturised HF-LPME device is presented in Paper I. The extraction method was developed for some weakly acidic pesticides and these were also used for evaluation. In the work described in Paper II, the method was optimised on the basis of an experimental design using spiked human plasma samples. Paper III presents a detailed study of the mass-transfer over the liquid membrane. The diffusion through the membrane pores was illustrated by a computer-simulation. Not surprisingly, the more lipophilic, the greater the retention of the compounds, as a result of dispersive forces. The main focus of the work described in Paper IV was to make the HF/LPME system more versatile and user-friendly; therefore, the extractor was automated by hyphenation to a SIA system. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript.

In dieser Arbeit werden verschiedene Verfahren vorgestellt, um Saturnpartikel herzustellen. Es wird die Selbstanordnung von erfolgreich hergestellten Saturnpartikeln untersucht. Im ersten Teil werden durch ein äquatoriales Ätzverfahren Saturnpartikel mit hydrophoben Kappen sowie einem hydrophilen Gürtel aus hydrophob beschichteten sphärischen Partikeln hergestellt. Mit einer Monolage dieser Saturnpartikel können Membranen aus Wasser (sogenannte Pickering-Membranen) stabilisiert werden. Die Pickering-Membranen sind über einen Zeitraum von mehreren Tagen stabil und lassen Permeabilitätsuntersuchungen zu. Diese Pickering-Membranen können als ein Spezialfall einer Supported Liquid Membrane angesehen werden. Es werden die Permeabilitätsunterschiede von Kohlenstoffdioxid gegen Luft sowie Luft gegen Schwefelhexafluorid betrachtet. Die resultierenden Werte stimmen in zufriedenstellender Weise mit theoretisch – nach dem für Supported Liquid Membranes gängigen Löslichkeits-Diffusionsmodell – berechneten Werten überein. Im zweiten Teil werden Partikel über Float-casting in Membranen eingebettet und dadurch rundherum – nicht jedoch an den Polkappen – äquatorial maskiert. Anschließend wird Gold aufgedampft und die maskierende Membran entfernt, sodass Saturnpartikel zurück bleiben. Die Saturnpartikel weisen hydrophile Kappen sowie einen hydrophoben Gürtel auf. An einer Öl-Wasser-Grenzfläche kommt es zu einer Selbstanordnung dieser Saturnpartikel durch Verknüpfung ihrer Gürtel in Form von zweidimensionalen Netzwerken. In diesen Netzwerken können einfache geometrische Formen gefunden werden. Es ist dabei nicht möglich, die Partikel durch einen Krafteintrag in einem flächendeckenden Muster zu organisieren. Die Untersuchung erfolgt durch konfokale Fluoreszenzspektroskopie. Die Goldkappen der Saturnpartikel zeigen ein Fluoreszenzsignal.:Bibliographische Beschreibung und Referat Danksagung Inhaltsverzeichnis Abkürzungsverzeichnis 1 Einleitung 2 Theoretischer Teil 2.1 Januspartikel 2.1.1 Herstellungsmöglichkeiten 2.1.1.1 Herstellung durch Oberflächenmodifizierung 2.1.1.2 Phasenseparation zweier nicht mischbarer Flüssigkeiten 2.1.1.3 Herstellung aus Bausteinen über Selbstanordnung 2.1.2 Anwendung 2.2 Saturnpartikel 2.2.1 Herstellung durch Oberflächenmodifizierung 2.2.2 Herstellung durch Phasenseparation von nicht mischbaren Flüssigkeiten 2.2.3 Herstellung aus Bausteinen über Selbstanordnung 2.3 Partikelstabilisierte Membranen 2.4 Aktuelle Fortschritte in der Gastrennung Mittels Gestützter Flüssigmembranen 2.4.1 Gestützte Flüssigmembranen (Supported Liquid Membranes) 2.4.2 Flüssigkeiten 2.4.2.1 Nicht-Ionische Flüssigkeiten 2.4.2.2 Ionische Flüssigkeiten 2.4.2.3 Stark Eutektische Lösemittel 2.4.3 Matrixmaterialien 2.4.4 Träger 2.4.5 Trennaufgaben 2.4.5.1 CO2/N2 2.4.5.2 CO2/CH4 2.4.5.3 Alken/Alkan 2.4.5.4 Andere Trennaufgaben 2.4.6 Einfluss von Temperatur und Druck 2.4.7 Stabilität 2.4.8 Simulationen 2.4.9 Zusammenfassung und Ausblick des Kapitels 2.5 Grenzflächen 2.5.1 Grenzflächenspannung 2.5.2 Kontaktwinkel und Benetzung 2.5.3 Partikelassistierte Benetzung 2.5.3.1 Float-casting 2.6 Modifizierung von Oberflächen durch Selbstorganisierende Monoschichten 2.6.1 Silanisierung von Oberflächen 2.6.2 Thiolisierung von Oberflächen 2.7 Fluoreszenz 2.8 Netzwerkanalyse 3 Ergebnisse und Diskussion 3.1 Herstellung von Saturnpartikeln durch schrittweises Einsinken in ein Polymer 3.2 Herstellung von Saturnpartikeln mit geätztem Ring mit Ätzzelle 3.2.1 Beschreibung der Ätzzelle 3.2.2 Optimierung des Verfahrens 3.2.2.1 Einlegen der Thermoplastischen Folien in Ethanol 3.2.2.2 Einführung eines Luer-Lock-Systems 3.2.2.3 Erhöhung der Pumpgeschwindigkeit bei der Reinigung 3.2.3 Beschreibung der erhaltenen Saturnpartikel 3.3 Pickering-Membranen stabilisiert durch Saturnpartikel mit geätztem Ring 3.3.1 Permeabilitätsuntersuchungen von Pickering-Membranen 3.3.1.1 Theoretische Permeanzen 3.3.1.2 Experimentelle Permeanzen 3.4 Herstellung von Saturnpartikeln durch Beschichtung mit Gold und graduelles Ätzen 3.5 Herstellung von Saturnpartikeln über Float-casting 3.5.1 Herstellung von Saturnpartikeln über Float-casting: Glaspartikel 3.5.2 Herstellung von Saturnpartikeln über Float-casting: Siliziumdioxidpartikel 3.5.3 Herstellung von Saturnpartikeln über Float-casting: Silsesquioxanpartikel 3.5.3.1 Bestimmung der Schichtdicke des Goldes 3.5.3.2 Membranherstellung mit Silsesquioxanpartikel über Floatcasting 3.5.3.3 Oberflächenmodifizierung der Goldkappen 3.6 Selbstanordnung von Saturnpartikeln unter dem Konfokalmikroskop 3.6.1 Erste Anordnungen 3.6.2 Einsatz von Zinkbromidlösungen 3.6.3 Fluoreszenz von Saturnpartikeln bei verschiedenen Flüssigkeitsgemischen 3.6.4 Fluoreszenz der Goldkappen 3.6.5 Flüssigkeitsmeniskus in den Probengefäßen 3.6.6 Messung an der Flüssig-Flüssig-Grenzfläche 3.6.7 Schallunterstützte Anordnung 3.6.8 Mathematische Beschreibung der Saturnpartikelnetzwerke 4 Zusammenfassung und Ausblick 5 Experimenteller Teil 5.1 Eingesetzte Chemikalien 5.2 Verwendete Geräte 5.3 Partikelsynthese und -oberflächenmodifikation 5.3.1 Herstellung von Siliziumdioxidpartikeln im Submikrometermaßstab 5.3.2 Herstellung von Polystyrolpartikeln im Mikrometermaßstab 5.3.3 Oberflächenmodifizierung von Glaspartikeln mit Silanen 5.4 Saturnpartikel durch schrittweises Einsinken in ein Polymer 5.5 Saturnpartikel durch Beschichtung mit Gold und graduelles Ätzen 5.6 Saturnpartikel mit geätztem Ring mit Ätzzelle 5.6.1 Pickering-Membranen in einem Rollrandgläschen 5.6.2 Pickering-Membranen in der Permeationsapparatur und Permeationsuntersuchungen 5.7 Saturnpartikeln über Float-Casting 5.7.1 Glaspartikel, Supelco Glass Beads 5.7.2 Siliziumdioxidpartikel, Stöberpartikel 5.7.3 Silsesquioxanpartikel, Tospearls 5.8 Kontaktwinkelmessungen 5.8.1 Kontaktwinkel von Partikeln 5.8.2 Kontaktwinkel von planaren Substraten 5.9 Konfokalmikroskopieaufnahmen 5.9.1 Fluoreszenzlösungen 5.9.2 Konfokalmikroskopieprobengefäße 5.9.3 Subwoofer 5.9.4 Messungen am Konfokalmikroskop 5.10 Rasterelektronenmikroskopieaufnahmen 5.11 Plasmaätzen Literaturverzeichnis Selbstständigkeitserklärung Lebenslauf Veröffentlichungen und Tagungsbeiträge

Membrane transport processes underlie many purification technologies. The efficiency of a membrane separation process depends upon material throughput (flux), and the degree to which the membrane discriminates amongst species in the feed stock (selectivity). In a supported liquid membrane, flux may be enhanced by carrier molecules, which act as catalysts of translocation. Carrier molecules also confer selectivity, via differential molecular recognition of the substances in the feed stock. The effect of electrical potential on the flux and selectivity of carrier-containing supported liquid membranes is not well documented. We elected to study the effect of electrical potential on supported liquid membranes containing valinomycin, a potassium ionophore, and a calixarene ester, a sodium ionophore. In these systems, the open circuit membrane potential could be made positive or negative by the choice of anion. With both of these carriers, we observed that selectivity for potassium or sodium salts was dependent on the open circuit membrane potential. To confirm that electrical potential was responsible for the observed selectivity variance, we applied a potential across the membrane using a potentiostat. The applied potential created conditions for carrier-mediated electrodialysis, where oxidation and reduction reactions on either side of the membrane act as the driving force for transmembrane flux of charged species. In chronoamperometry experiments, we found that selectivity for potassium or sodium ion was dependent on the applied electrical potential. Subject to some constraints, selectivity and flux could be controlled by the application of positive or negative electrical potentials. Linear sweep voltammetry experiments allowed for the rapid prediction of the potential that must be applied to achieve optimal selectivity. We also found that membrane potential measurements, as well as the magnitude of current that flows in chronoamperometry experiments, could be interpreted to predict Eisenman and Hofmeister sequences. These results are novel, and await a convincing theoretical justification. The results also suggest that a separation technology could be developed around the idea of modulating selectivity with electrical potential. In this regard, carrier-mediated electrodialysis may be suitable for the sequestration of toxic or radioactive heavy metals, and a large number of carrier molecules for metal ions are currently known. The technique may also be suitable for separating organic molecules, such as high-value chiral pharmaceuticals. Supported liquid membranes are a useful research tool, but industrial applications may require a more stable membrane architecture. / Graduate

The presented thesis investigates the transfer of drug molecules across interfaces that mimic biological membrane barriers. The permeability of drug molecules across biological membrane mimics has been investigated in a novel artificial membrane permeation assay configuration using an in situ time-dependent approach and reproducible rotation of the membrane. A method to determine the membrane permeability from the knowledge of measured permeability and the applied stirring rate is presented. The initial transient of the permeation response, previously not observed in situ, is investigated and its importance in data evaluation is discussed. The permeability coefficients of 31 drugs are optimised for the conditions found in vivo and a correlation with the fraction absorbed in humans is presented. The evidence for ionic and/or ion-pair flux across the artificial membrane obtained from measurement of permeability at different pH is supported by the investigation of the permeation assay with external membrane polarisation. The permeability coefficient of the solute's anionic form is determined. Liquid/liquid electrochemistry has been used to study the transfer of ionized species across the interface between water and 1,2-dichloroethane. An alternative method to study the transfer of partially ionised drug molecules employing a rotating liquid/liquid interface is presented. In addition, a bipolar electrochemical cell with a rotating-disc electrode is developed and its properties investigated in order to verify the hydrodynamics of the rotating artificial membrane configuration. Finally, in support of the electrochemical techniques used is this thesis, a detailed preparation and evaluation of the silver/silver sulphate reference electrode is presented.

The thesis presents experimental study on application of various polypropylene membranes (with different thicknesses, porosity and pore size) for direct coupling of membrane microextractions with capillary electrophoresis. No comprehensive study, which describes effect of these membrane parameters on extraction recoveries, was published in the past. Previous scientific works prefer application of 100 µm polypropylene membranes for their easy handling and satisfactory extraction efficiencies. Experimental part includes examination of selected polypropylene membranes as supported liquid membranes in-line coupled to capillary electrophoresis for analysis of basic drugs from complex samples. Membranes with three thicknesses (25, 100 and 170 µm) were tested. The highest extraction recoveries were achieved for the 25µm thick polypropylene membrane. Various pH conditions of donor and acceptor operational solutions were examined for extractions from real complex matrices (urine, plasma). The optimal extraction conditions were 10 mM NaOH as donor phase and 10 mM HCl as acceptor phase. 25µm membranes offer higher extraction recoveries, reduced consumption of organic solvents for membrane impregnation, similar mechanical stability and similar clean-up ability compared to thicker polypropylene membranes.

This thesis focuses on low-cost microextraction techniques and their application for purification and preconcentration of biological samples, specifically on the experimental study of supported liquid membrane (SLM) extraction. The described microextraction technique uses commercially available filtration plates as the extraction units and allows the extraction of basic drugs from biological samples of urine and blood (in the form of dried blood spots). The experimental part includes the optimization of microextraction conditions of basic drugs from real samples through a SLM coupled in-line to lab-made capillary electrophoresis. The basic optimization of microextraction conditions involved selecting the appropriate organic phase for membrane impregnation (1:1 mixture of ENB and DHE), appropriate agitation speed for sample convection during extraction (1000 rpm), and optimal ratio of donor to acceptor volumes for high preconcentration of the analytes (400:15 µL). After basic optimization, the effect of donor alkalization with NaOH on extraction recovery (ER) was investigated. For all matrices used (saline solution, undiluted human urine samples, human capillary blood eluted from dry blood spots with deionized water), the highest ER values were achieved using a neutral donor and an acidic acceptor. The extraction time (60 minutes) was optimized based on the time profile of the microextraction for 120 minutes. This optimized microextraction method is suitable for the determination of basic drugs in real matrices with sufficient sample clean-up, preconcentration and ER values.